KR101534054B1 - Poly(arylene ether) composition and extruded articles derived therefrom - Google Patents

Abstract

(Arylene ether) -polysiloxane block copolymer comprising a hydrogenated block copolymer of a conjugated diene with an alkenyl aromatic compound, a flame retardant, and a poly (arylene ether) -polysiloxane block copolymer itself (Arylene ether). ≪ / RTI > The poly (arylene ether) -polysiloxane block copolymer contributes to the improvement of the flame retardancy and in many cases the improvement of the physical properties of the composition.

Description

POLY (ARYLENE ETHER) COMPOSITION AND EXTRUDED ARTICLES DERIVED THEREFROM < RTI ID = 0.0 >

The present invention relates to poly (arylene ether) compositions and extrudates derived therefrom.

Poly (arylene ether) resins are a type of plastic known to have excellent water resistance, dimensional stability, and high flame retardancy. Properties such as strength, stiffness, chemical resistance, and heat resistance can be used to meet the requirements of a wide variety of consumer products such as, for example, pipe fixtures, electric boxes, automotive parts, By blending with various other plastics.

Poly (vinyl chloride), a different plastic, is currently a commercially leading material for flame retardant wire and cable insulation. However, poly (vinyl chloride) is a halogenated material. There is a growing interest in the environmental impact of halogenated materials, and non-halogenated alternatives are sought. Thus, there is a strong desire to replace poly (vinyl chloride) with a non-halogenated polymer composition - a legal order in some places.

Recent research has shown that certain halogen-free poly (arylene ether) compositions can have the physical properties and flame retardancy required for use as wire and cable insulation. Reference is made to US Patent Application Publication US 2006/0106139 A1 and US 2006/0182967 A1 by Kosaka et al. The compositions disclosed in this patent document can exhibit good flame retardancy and good physical properties such as flexibility and tensile stress at break. The poly (arylene ether) component itself of these compositions is relatively flame retardant, but significant amounts of other flame retardants are typically added to ensure that the entire composition is sufficiently flame retardant. The trade-off of physical properties typically requires relatively large amounts of flame retardants. For example, when the flame retardant composition contains a metal hydroxide such as a significant amount of magnesium hydroxide, flexibility (e.g., as measured by the target tensile elongation) is reduced. As another example, when the flame retardant composition comprises a significant amount of a liquid organophosphate flame retardant, the flame retardant may migrate to the surface of the insulation and cause aesthetic problems, and more importantly, reduce the flame retardancy of the composition. Accordingly, there is a need for flame retardant poly (arylene ether) compositions that exhibit an improved balance of flame retardancy, physical properties, and aesthetic properties.

It is an object of the present invention to provide a flame retardant poly (arylene ether) composition that overcomes the problems of the prior art and balances flame retardancy, physical properties and aesthetic properties.

Poly (arylene ether) homopolymer, and

(Arylene ether) -polysiloxane block copolymer comprising a poly (arylene ether) block and a polysiloxane block comprising an average of 35 to 80 siloxane repeat units

(Arylene ether) -polysiloxane block copolymer reaction product comprising from 5 to 55% by weight of a poly (arylene ether) -polysiloxane block copolymer reaction product,

 10 to 55% by weight hydrogenated block copolymer of a conjugated diene with an alkenyl aromatic compound; And

2 to 25 wt%

≪ / RTI >

Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product comprises 1-8 wt% siloxane repeat units and 92-99 wt% arylene ether repeat units;

Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product is a product of a process comprising oxidation of a monomer mixture comprising a monohydric phenol and a hydroxyaryl-terminated polysiloxane in an oxidative manner;

The poly (arylene ether) -polysiloxane block copolymer reaction product has a weight average molecular weight of at least 30,000 atomic mass units,

All of the above weight percentages are based on the total weight of the composition, the aforementioned problems and other disadvantages are overcome.

Another embodiment is an extruded or injection molded article,

Poly (arylene ether) homopolymer, and

(Arylene ether) -polysiloxane block copolymer comprising a poly (arylene ether) block and a polysiloxane block comprising an average of 35 to 80 siloxane repeat units

(Arylene ether) -polysiloxane block copolymer reaction product comprising from 5 to 55% by weight of a poly (arylene ether) -polysiloxane block copolymer reaction product,

 10 to 55% by weight hydrogenated block copolymer of a conjugated diene with an alkenyl aromatic compound; And

2 to 25 wt%

≪ / RTI >

Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product comprises 1-8 wt% siloxane repeat units and 92-99 wt% arylene ether repeat units;

Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product is a product of a process comprising oxidizing a monomer mixture comprising a monovalent phenol and a hydroxyaryl-terminated polysiloxane in an oxidative manner;

The poly (arylene ether) -polysiloxane block copolymer reaction product has a weight average molecular weight of at least 30,000 atomic mass units,

Wherein all of said weight percentages are based on the total weight of said composition.

Which is an extrusion or injection-molded product of the composition.

These and other implementations are described in detail below.

In accordance with the present invention, a flame retardant poly (arylene ether) composition is provided that balances flame retardancy, physical properties and aesthetic properties.

The present inventors have found that the substitution of certain poly (arylene ether) -polysiloxane block copolymers for some of the poly (arylene ether) homopolymers in a composition comprising a hydrogenated block copolymer and a flame retardant improves flame retardancy, ≪ / RTI > improves the physical properties of the composition. Improvements in flame retardancy can be used to lower flame retardant levels and further improve physical and aesthetic properties. As demonstrated in the working examples below, this advantage is not obtained when an equivalent amount of polysiloxane is added to the composition. Thus, significant unexpected advantages are obtained from the use of poly (arylene ether) -polysiloxane block copolymers.

One embodiment is a poly (arylene ether) -polysiloxane block copolymer comprising a poly (arylene ether) homopolymer and a poly (arylene ether) block and a polysiloxane block comprising an average of 35-80 siloxane repeat units 5 to 55% by weight of a poly (arylene ether) -polysiloxane block copolymer reaction product comprising a polymer; 10 to 55% by weight hydrogenated block copolymer of a conjugated diene with an alkenyl aromatic compound; And 2-25 wt% of a flame retardant, wherein the poly (arylene ether) -polysiloxane block copolymer reaction product comprises 1-8 wt% siloxane repeat units and 92-99 wt% arylene ether repeat units Include; Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product is a product of a process comprising oxidizing a monomer mixture comprising a monovalent phenol and a hydroxyaryl-terminated polysiloxane in an oxidative manner; Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product has a weight average molecular weight of at least 30,000 atomic mass units, all the weight percentages being based on the total weight of the composition.

An important component of the composition of the present invention is a poly (arylene ether) -polysiloxane block copolymer. This component is synthesized by oxidative polymerization of a monomer mixture comprising a monovalent phenol and a hydroxyaryl-terminated polysiloxane. This oxidation-type polymerization produces a poly (arylene ether) -polysiloxane block copolymer as a product to be obtained and a poly (arylene ether) (not containing a polysiloxane block) as a by-product. Separation of a poly (arylene ether) from a poly (arylene ether) -polysiloxane block copolymer is both difficult and unnecessary. Thus, the poly (arylene ether) -polysiloxane block copolymer is incorporated into the composition of the present invention as a "reaction product " comprising both a poly (arylene ether) and a poly (arylene ether) -polysiloxane block copolymer . By a specific separation process, such as precipitation from isopropanol, it can be ensured that the reaction product is essentially free of residual hydroxyaryl-terminated polysiloxane starting material. That is, this separation process ensures that the polysiloxane portion of the reaction product is essentially entirely in the form of a poly (arylene ether) -polysiloxane block copolymer.

The poly (arylene ether) -polysiloxane block copolymer reaction product may be a poly (arylene ether); And a poly (arylene ether) -polysiloxane block copolymer comprising a polysiloxane block comprising a poly (arylene ether) block and an average of 35 to 80 siloxane repeat units; Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product comprises 1-8 wt% siloxane repeat units and 92-99 wt% arylene ether repeat units; Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product is a product of a process comprising oxidizing a monomer mixture comprising a monovalent phenol and a hydroxyaryl-terminated polysiloxane in an oxidative manner; The poly (arylene ether) -polysiloxane block copolymer reaction product has a weight average molecular weight of 30,000 atomic mass units or more.

The poly (arylene ether) -polysiloxane block copolymer reaction product comprises poly (arylene ether). Poly (arylene ether) is a product obtained by polymerizing monovalent phenol alone, and is a by-product of the synthesis of block copolymers. When the monohydric phenol is composed of a single compound (for example, 2,6-dimethylphenol), the poly (arylene ether) is the product of the homopolymerization of the monovalent phenol. When the monovalent phenol comprises two or more distinct monovalent phenol species (for example, a mixture of 2,6-dimethylphenol and 2,3,6-trimethylphenol), the poly Is a product obtained by copolymerizing two or more distinct monovalent phenol species. By the nuclear magnetic resonance method described in the working examples, it was not possible to place the phenylene ether moiety between the poly (arylene ether) and the poly (arylene ether) -polysiloxane block copolymer. However, the presence of a poly (arylene ether) can be achieved by a "tail" group as defined below (eg, a 2,6-dimethylphenoxy group when the monovalent phenol is 2,6-dimethylphenol), and / From the detection and quantification of the presence of the "biphenyl" group (eg, 3,3 ', 5,5'-tetramethyl-4,4'-biphenol) defined below in the product.

In addition to the poly (arylene ether), the poly (arylene ether) -polysiloxane block copolymer reaction product comprises a poly (arylene ether) -polysiloxane block copolymer. The poly (arylene ether) -polysiloxane block copolymer comprises a poly (arylene ether) block and a polysiloxane block. The poly (arylene ether) block is a residue of the polymerization of a monovalent phenol. In some embodiments, the poly (arylene ether) block comprises an arylene ether repeat unit having the structure:

Wherein in each repeating unit, each Z ¹ is independently halogen, Beach cyclic or substitutional C ₁ -C ₁₂ hydrocarbyl, with the proviso that the hydrocarbyl group is not a tertiary hydrocarbyl, C ₁ - C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbyloxy, or C ₂ -C ₁₂ halo hydrocarbyloxy, wherein two or more carbon atoms separate hydrogen and oxygen atoms; Each Z ² is independently hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl, provided that the hydrocarbyl group is not a tertiary hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbyloxy, or C ₂ -C ₁₂ halo hydrocarbyloxy, wherein two or more carbon atoms separate hydrogen and oxygen atoms. The term "hydrocarbyl ", as used herein, refers to a moiety that contains only carbon and hydrogen, whether used by itself or as a prefix, suffix, or part of another term. The moiety may be aliphatic or aromatic and may be linear, cyclic, bicyclic, branched, saturated or unsaturated. The moieties may also contain combinations of aliphatic, aromatic, linear, cyclic, bicyclic, branched, saturated or unsaturated hydrocarbon moieties. When the hydrocarbyl residue is described as being substituted, it may optionally contain a heteroatom on the carbon and hydrogen member of the substituent moiety. Thus, when described as substitutionally specified, the hydrocarbyl moieties may also include one or more substituents such as halogen (including fluorine, chlorine, bromine, and iodine), carboxylic acid groups, amino groups, hydroxyl groups, May contain a divalent heteroatom-containing group such as an oxygen atom, a silicon atom, and a carbonyl group in the skeleton of the benzyl group. In some embodiments, the poly (arylene ether) block is a 2,6-dimethyl-1,4-phenylene ether repeat unit, i.e., a repeat unit having the following structure:

Or 2,3,6-trimethyl-1,4-phenylene ether repeating unit, or a combination thereof.

The polysiloxane block is a residue of a hydroxyaryl-terminated polysiloxane. In some embodiments, the polysiloxane block comprises a repeating unit having the structure:

Wherein each R ¹ and R ² is independently hydrogen, C ₁ -C ₁₂ hydrocarbyl or C ₁ -C ₁₂ halo hydrocarbyl; The polysiloxane block further comprises a terminal unit having the structure:

Formula, Y is hydrogen, C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbyl-oxy, or halogen, each of R ³ and R ⁴ are independently hydrogen, C ₁ -C ₁₂ hydrocarbyl Or C ₁ -C ₁₂ halohydrocarbyl. In some embodiments, R ¹ and R ² are C ₁ -C ₆ alkyl, specifically C ₁ -C ₃ alkyl, more particularly methyl. In some embodiments, the polysiloxane repeating unit include dimethylsiloxane _{(-Si (CH 3) 2 O-} ) units. In some embodiments, the polysiloxane block has the following structure:

In the formula, n is 35 to 60.

In some embodiments, the poly (arylene ether) block comprises an arylene ether repeat unit having the structure:

And polysiloxane blocks having the structure:

N is from 35 to 60; The poly (arylene ether) -polysiloxane block copolymer reaction product has a number average molecular weight of 10,000 to 30,000 atomic mass units.

The hydroxyaryl-terminated polysiloxane comprises at least one hydroxyaryl end group. In some embodiments, the hydroxyaryl-terminated polysiloxane has one hydroxyaryl end group, in which case a poly (arylene ether) -polysiloxane diblock copolymer is formed. In another embodiment, the hydroxyaryl-terminated polysiloxane has two hydroxyaryl end groups, in which case a poly (arylene ether) -polysiloxane diblock and / or triblock copolymer is formed. The hydroxyaryl-terminated polysiloxane may have a branched structure to have three or more hydroxyaryl end groups and may allow the formation of corresponding branched copolymers.

As mentioned earlier, the polysiloxane block copolymer contains on average 35 to 80 siloxane repeat units. Within this range, the number of siloxane repeating units may be from 35 to 60, more specifically from 40 to 50. The number of siloxane repeat units in the polysiloxane block is essentially unaffected by the copolymerization and separation conditions and thus the number corresponds to the number of siloxane repeat units in the hydroxyaryl-terminated polysiloxane starting material. Unless otherwise known, the average number of siloxane repeating units per molecule of hydroxyaryl-terminated polysiloxane is determined by NMR method, comparing the intensity of the signal associated with the siloxane 1 repeating unit and the signal associated with the hydroxyaryl terminal group ≪ / RTI > For example, when the hydroxyaryl-terminated polysiloxane is eugenol-capped polydimethylsiloxane, the proton nuclear magnetic resonance, which compares the integrals of protons of dimethylsiloxane resonance with those of the eugenol methoxy group, ( ¹ H NMR) method, the average number of siloxane repeating units can be determined.

The poly (arylene ether) -polysiloxane block copolymer reaction product comprises, based on the total weight of the poly (arylene ether) -polysiloxane block copolymer reaction product, 1 to 8 weight percent siloxane repeat units and 92 to 99 weight percent arylene Ether repeating units. Within this range, the weight percent of siloxane repeat units can be from 3 to 7 wt%, specifically from 4 to 6 wt%, more specifically from 4 to 5 wt%; The weight percentage of the arylene ether repeating unit may be 93 to 97 wt%, specifically 94 to 96 wt%, more specifically 95 to 96 wt%.

As mentioned previously, the poly (arylene ether) -polysiloxane block copolymer reaction product is a product of the process comprising an oxidatively copolymerizing a monomer mixture comprising monovalent phenol and hydroxyaryl-terminated polysiloxane . Thus, the poly (arylene ether) -polysiloxane block copolymer reaction product is prepared by a simpler method than the poly (arylene ether) -polysiloxane block copolymer synthesis method which requires the coupling of a polysiloxane block with a preformed poly (arylene ether) Lt; / RTI >

The poly (arylene ether) -polysiloxane block copolymer reaction product has a weight average molecular weight of at least 30,000 atomic mass units. In some embodiments, the weight average molecular weight is from 30,000 to 150,000 atomic mass units, specifically from 35,000 to 120,000 atomic mass units, more specifically from 40,000 to 90,000 atomic mass units, and more specifically from 45,000 to 70,000 atomic mass units. In some embodiments, the poly (arylene ether) -polysiloxane block copolymer reaction product has a number average molecular weight of 10,000 to 50,000 atomic mass units, specifically 10,000 to 30,000 atomic mass units, more specifically 14,000 to 24,000 atomic mass units Of the number average molecular weight. Specific chromatographic methods for determining molecular weight are described in the working examples below.

The poly (arylene ether) -polysiloxane block copolymer reaction product may comprise a relatively small amount of very low molecular weight species. Thus, in some embodiments, the poly (arylene ether) -polysiloxane block copolymer reaction product has a molecular weight less than 25 weight percent, specifically less than 10,000 atomic weight units, with a molecular weight less than 10,000 atomic mass units By weight of molecules having a molecular weight of less than 10,000 atomic mass units, and more preferably from 7 to 21% by weight of molecules having molecular weights of less than 10,000 atomic mass units. In some embodiments, molecules with a molecular weight of less than 10,000 atomic mass units comprise, on average, 5 to 10 weight percent siloxane repeat units, specifically 6 to 9 weight percent siloxane repeat units.

Likewise, the poly (arylene ether) -polysiloxane block copolymer reaction product may also comprise a relatively small amount of very high molecular weight species. Thus, in some embodiments, the poly (arylene ether) -polysiloxane block copolymer reaction product has a molecular weight greater than 25 weight percent, specifically greater than 100,000 atomic mass units, with a molecular weight greater than 100,000 atomic mass units 5 to 25% by weight of molecules having a molecular weight greater than 100,000 atomic mass units, and 7 to 23% by weight of molecules having molecular weights of more than 100,000 atomic mass units. In some embodiments, molecules with molecular weights greater than 100,000 atomic mass units comprise on average, 3 to 6 weight percent siloxane repeat units, specifically 4 to 5 weight percent siloxane repeat units.

In some embodiments, the poly (arylene ether) -polysiloxane block copolymer reaction product has an intrinsic viscosity of at least 0.3 dl / g measured in chloroform at 25 ° C. The intrinsic viscosity may be 0.3 to 0.6 dl / g, specifically 0.3 to 0.5 dl / g, more specifically 0.31 to 0.55 dl / g, and more specifically 0.35 to 0.47 dl / g.

One indication of the efficiency with which the hydroxyaryl-terminated polysiloxane is incorporated into the block copolymer is the so-called low concentration poly (arylene ether) "tail" group. In the homopolymerization of 2,6-dimethylphenol, a large proportion of the product molecules have a so-called head-to-tail structure in which the linear product molecules are 3,5-dimethyl- The end is terminated by the Roxiphenyl "head" and the other end is terminated by 2,6-dimethylphenoxy "tail ". Thus, when the monovalent phenol is composed of 2,6-dimethylphenol, the poly (arylene ether) tail group has the following structure:

In the formula, the 3-, 4-, and 5-positions of the ring are substituted with hydrogen atoms (i.e., the term 2,6-dimethylphenoxy includes the divalent 2,6-dimethyl-1,4-phenylene ether group I never do that). In the copolymerization of a monovalent phenol and a hydroxyaryl-terminated polysiloxane, incorporation of the hydroxyaryl-terminated polysiloxane into the block copolymer will reduce the concentration of the arylene ether "tail" group. When the monohydric phenol is composed of 2,6-dimethylphenol, and in particular when the poly (arylene ether) -polysiloxane block copolymer reaction product is the sole source of polyphenylene ether in the composition, , 0.4 wt% or less, specifically 0.2 to 0.4 wt% of 2,6-dimethylphenoxy group. When the monohydric phenol is composed of 2,6-dimethylphenol, and in particular when the composition further comprises a poly (arylene ether) in addition to being present in the poly (arylene ether) -polysiloxane block copolymer reaction product , The composition comprises not more than 1% by weight, specifically 0.2 to 1% by weight, of the 2,6-dimethylphenoxy group, based on the weight of the composition.

The poly (arylene ether) -polysiloxane block copolymer reaction product may further comprise a group derived from diphenoquinone, which is itself an oxidation product of a monovalent phenol. For example, when the monohydric phenol is 2,6-dimethylphenol, the poly (arylene ether) -polysiloxane block copolymer reaction product comprises 1.1-2.0 wt% 2,6-dimethyl-4- (3,5- Dimethyl-4-hydroxyphenyl) phenoxy group.

The poly (arylene ether) -polysiloxane block copolymer reaction product can be separated from the solution by a separation process that minimizes volatile and non-volatile contaminants. For example, in some embodiments, the poly (arylene ether) -polysiloxane block copolymer reaction product has a total volatility of less than or equal to 1 wt%, specifically from 0.2 to 1 wt%, as determined according to the process of the working examples below ≪ / RTI > In some embodiments, the monomer mixture is oxidatively copolymerized in the presence of a catalyst comprising a metal (e.g., copper or manganese) and the poly (arylene ether) -polysiloxane block copolymer reaction product comprises less than 100 ppm by weight metal, Specifically 0.5 to 100 ppm by weight of the metal, more specifically 10 to 50 ppm by weight of the metal, more specifically 20 to 50 ppm by weight of the metal.

The poly (arylene ether) -polysiloxane block copolymer reaction product is prepared by oxidatively copolymerizing a monovalent phenol and a hydroxyaryl-terminated polysiloxane to form a poly (arylene ether) -polysiloxane block copolymer reaction product ≪ / RTI > The oxidation-type copolymerization can be initiated in the presence of at least 50% by weight of hydroxyaryl-terminated polysiloxane and up to 50% by weight of monovalent phenol. In some embodiments, the oxidation-type copolymerization is accomplished by at least 80 weight percent hydroxyaryl-terminated polysiloxane, specifically at least 90 weight percent hydroxyaryl-terminated polysiloxane, more specifically at least 100 weight percent hydroxyaryl- Lt; / RTI > polysiloxane.

The oxidation-type copolymerization can be carried out with a reaction time of 110 minutes or more.

The hydroxyaryl-terminated polysiloxane may comprise from 35 to 80 siloxane repeating units on average. In some embodiments, the hydroxyaryl-terminated polysiloxane comprises an average of 40-70 siloxane repeat units, specifically 40-60 siloxane repeat units, more specifically 40-50 siloxane repeat units. The hydroxyaryl-terminated polysiloxane may have a total weight of 1 to 8% by weight, specifically 3 to 8% by weight, of a monovalent phenol and a hydroxyaryl-terminated polysiloxane.

The oxidation of the oxidation system can be carried out at a reaction time of 110 minutes or more. The reaction time is the elapsed time between the beginning and end of the oxygen flow. (For brevity, the description herein repeatedly refers to "oxygen" or "oxygen flow", but it will be appreciated that any oxygen-containing gas, including air, can be used as the oxygen source.) In some implementations , The reaction time is 110 to 300 minutes, specifically 140 to 250 minutes, more specifically 170 to 220 minutes.

The oxidation-type copolymerization may include a "build time" which is the time between completion of monomer addition and termination of the oxygen flow. In some embodiments, the reaction time includes a build time of 80-160 minutes. In some embodiments, the reaction temperature during at least a portion of the build time may be 40-60 캜, specifically 45-55 캜.

After the copolymerization reaction is terminated, the product poly (arylene ether) -polysiloxane block copolymer reaction product can be separated from the solution using known methods for separating the poly (arylene ether) from the solution. For example, the poly (arylene ether) -polysiloxane block copolymer reaction product may be separated by precipitation with an antisolvent such as a C ₁ -C ₆ alkanol, including methanol, ethanol, n-propanol and isopropanol . The inventors have found that it is advantageous to use isopropanol because isopropanol is a good solvent for unreacted hydroxyaryl-terminated polysiloxanes. Thus, precipitation and washing with isopropanol substantially removes the hydroxyaryl-terminated polysiloxane from the separated product. As an alternative to precipitation, the poly (arylene ether) -polysiloxane block copolymer reaction product can be separated by a direct separation method involving devolatilization. In some embodiments, the composition comprises less than or equal to 1.5% by weight, specifically less than or equal to 0.5% by weight, hydroxy aryl-terminated polysiloxane, based on the total weight of the composition. It has been observed that the precipitation of the poly (arylene ether) -polysiloxane block copolymer reaction product in isopropanol is effective in separating the hydroxyaryl-terminated polysiloxane from the reaction product.

In some embodiments, the poly (arylene ether) -polysiloxane block copolymer reaction product incorporates a hydroxy aryl-terminated polysiloxane starting material in an amount greater than 75 weight percent into the poly (arylene ether) -polysiloxane block copolymer . Specifically, the amount of the hydroxyaryl-terminated polysiloxane incorporated into the poly (arylene ether) -polysiloxane block copolymer is at least 80 wt%, more specifically at least 85 wt%, more specifically at least 90 wt% More specifically at least 95% by weight.

In a very specific process for preparing the poly (arylene ether) -polysiloxane block copolymer reaction product, the monovalent phenol is 2,6-dimethylphenol; The hydroxyaryl-terminated polysiloxane is a eugenol-capped polydimethylsiloxane comprising 35 to 60 dimethylsiloxane units; The oxidative copolymerization is initiated in the presence of at least 90 weight percent hydroxyaryl-terminated polysiloxane and 2 to 20 weight percent monovalent phenol; The oxidative copolymerization is carried out at a reaction time of from 170 to 220 minutes; The hydroxyaryl-terminated polysiloxane constitutes from 2 to 7% by weight of the total weight of the monohydric phenol and the capped polysiloxane.

Further details regarding the preparation, characterization and characterization of the poly (arylene ether) -polysiloxane block copolymer reaction product are found in co-pending U. S. Patent Application No. 12 / 277,835, filed November 25, 2008 can see.

The composition comprises the poly (arylene ether) -polysiloxane block copolymer reaction product in an amount of 5 to 55 wt%, specifically 25 to 50 wt%, more specifically 30 to 45 wt%, based on the total weight of the composition, More specifically in an amount of 33 to 42% by weight.

The composition may comprise a poly (arylene ether) in addition to being derived from a poly (arylene ether) -polysiloxane block copolymer reaction product. For example, the composition may comprise the additional poly (arylene ether) in an amount of from 1 to 35% by weight, specifically from 5 to 30% by weight, more specifically from 10 to 25% by weight, based on the total weight of the composition . In the analysis of the complete composition, it is difficult to distinguish poly (arylene ether) derived from the poly (arylene ether) -polysiloxane block copolymer reaction product from poly (arylene ether) separately added to the composition, It may be useful to specify a "total poly (arylene ether)" comprising a poly (arylene ether) molecule and a poly (arylene ether) block of a poly (arylene ether) -polysiloxane block copolymer reaction product. Thus, the composition is present in an amount of from 20 to 55% by weight, specifically from 25 to 50% by weight, more specifically from 30 to 45% by weight, more specifically from 33 to 42% by weight, based on the total weight of the composition, (Arylene ether).

In addition to the poly (arylene ether) -polysiloxane block copolymer reaction product, the composition comprises a hydrogenated block copolymer of a co-lyophilic diene with an alkenyl aromatic compound. For brevity, this component is referred to herein as a "hydrogenated block copolymer ". The hydrogenated block copolymer may comprise a poly (alkenyl aromatic) content of 10 to 90 wt.% And a hydrogenated poly (co-lyptated diene) content of 90 to 10 wt.%. In some embodiments, the poly (alkenyl aromatic) content is 10-45 wt%, specifically 20-40 wt%. In another embodiment, the poly (alkenyl aromatic) content is 45 wt% to 90 wt%, specifically 45 to 80 wt%. The hydrogenated block copolymer may have a weight average molecular weight of from 40,000 to 400,000 atomic mass units. The number average molecular weight and the weight average molecular weight can be determined by gel permeation chromatography based on a comparison with a polystyrene standard. In some embodiments, the hydrogenated block copolymer has a weight average molecular weight of 200,000 to 400,000 atomic mass units, specifically 220,000 to 350,000 atomic mass units. In other embodiments, the hydrogenated block copolymer may have a weight average molecular weight of less than 40,000 to less than 200,000 atomic mass units, specifically 40,000 to 180,000 atomic mass units, more specifically 40,000 to 150,000 atomic mass units.

The alkenyl aromatic monomer used in the preparation of the hydrogenated block copolymer may have the following structure:

In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom, a C ₁ -C ₈ alkyl group, or a C ₂ -C ₈ alkenyl group; R ⁷ and R ¹¹ each independently represent a hydrogen atom, a C ₁ -C ₈ alkyl group, a chlorine atom, or a bromine atom; R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a C ₁ -C ₈ alkyl group, or a C ₂ -C ₈ alkenyl group, or R ⁸ and R ⁹ , together with the central aromatic ring, Or R ⁹ and R ¹⁰ together with the central aromatic ring form a naphthyl group. Particular alkenyl aromatic monomers include, for example, chlorostyrene such as styrene, p-chlorostyrene; And methylstyrenes such as alpha-methylstyrene and p-methylstyrene. In some embodiments, the alkenyl aromatic monomer is styrene.

The conjugated dienes used in the preparation of the hydrogenated block copolymers may be C ₄ -C ₂₀ conjugated dienes. Examples of suitable conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2,3- , 3-pentadiene, 1,3-hexadiene, and the like, and combinations thereof. In some embodiments, the conjugated diene is 1,3-butadiene, 2-methyl-1,3-butadiene, or a combination thereof. In some embodiments, the conjugated diene is 1,3-butadiene.

The hydrogenated block copolymer is a copolymer comprising at least one block derived from (A) an alkenyl aromatic compound and (B) at least one block derived from (A) a conjugated diene, and wherein the aliphatic unsaturated moiety in block And is at least partially reduced by hydrogenation. In some embodiments, the aliphatic unsaturation in the (B) block is reduced by 50% or more, specifically 70% or more. The arrays of blocks (A) and (B) include a linear structure, a grafted structure, and a radial teleblock structure with or without branches. The linear block copolymer includes a tapered linear structure and a non-tapered linear structure. In some embodiments, the hydrogenated block copolymer has a tapered straight-line structure. In some embodiments, the hydrogenated block copolymer has a non-tapered straight-line structure. In some embodiments, the hydrogenated block copolymer comprises a B block comprising random incorporation of an alkenyl aromatic monomer. The linear block copolymer structure includes not only diblock (AB block), triblock (ABA block or BAB block), tetrablock (ABAB block), and pentablock (ABABA or BABAB block) The molecular weight of each of the A blocks may be the same as or different from the molecular mass of the other A blocks and the molecular weight of each of the B blocks may be the same as or different from that of the other B blocks. In some embodiments, the hydrogenated block copolymer is a diblock copolymer, a triblock copolymer, or a combination thereof.

In some embodiments, the hydrogenated block copolymer excludes residues of monomers other than alkenyl aromatic compounds and conjugated dienes. In some embodiments, the hydrogenated block copolymer is composed of blocks derived from a conjugated diene with an alkenyl aromatic compound. The hydrogenated block copolymer does not contain grafts formed from these monomers or any other monomers. In addition, the hydrogenated block copolymer is composed of carbon and hydrogen atoms, and thus the heteroatoms are excluded.

In some embodiments, the hydrogenated block copolymer includes residues of one or more acid functionalizing agents such as maleic anhydride.

In some embodiments, the hydrogenated block copolymer comprises a polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer.

In some embodiments, the hydrogenated block copolymer comprises a polystyrene-poly (ethylene-butylene-styrene) -polystyrene triblock copolymer.

In some embodiments, the hydrogenated block copolymer includes a polystyrene-poly (ethylene-butylene-styrene) -polystyrene triblock copolymer and a polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer.

Processes for preparing hydrogenated block copolymers are already known, and many hydrogenated block copolymers are commercially available. Examples of commercially available hydrogenated block copolymers include polystyrene-poly (ethylene-propylene) diblock copolymers available as KRATON G1701 and G1702 from Kraton Polymers; Poly (ethylene-styrene) copolymers available from Kraton Polymers, Inc. as KRATON G1641, G1650, G1651, G1654, G1657, G1726, G4609, G4610, GRP-6598, RP-6924, MD-6932M, MD- Butylene) -polystyrene triblock copolymer; (Ethylene-butylene-styrene) -polystyrene (S-EB / SS) triblock copolymer, available as KRATON RP-6935 and RP-6936 from Kraton Polymers, polystyrene available as KRATON G1730 from Kraton Polymers Poly (ethylene-propylene) -polystyrene triblock copolymers; A maleic anhydride-grafted polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer available from Kraton Polymers as KRATON G1901, G1924, and MD-6684; A maleic anhydride-grafted polystyrene-poly (ethylene-butylene-styrene) -polystyrene triblock copolymer available from KRATON Polymers as KRATON MD-6670; Polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer containing 67% by weight of polystyrene available from Asahi Kasei Elastomer, available as TUFTEC H1043; A polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer containing 42% by weight of polystyrene available from Asahi Kasei Elastomer, available as TUFTEC H1051; Polystyrene-poly (butadiene-butylene) -polystyrene triblock copolymers available as TUFTEC P1000 and P2000 from Asahi Kasei Elastomer; Polystyrene-polybutadiene-poly (styrene-butadiene) -polystyrene block copolymer available from S.A.E.-SS L601 from Asahi Kasei Elastomer; Hydrogenated radial block copolymers available as K-Resin KK38, KR01, KR03, and KR05 from Chevron Phillips Chemical Company; Polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer containing 60% by weight of polystyrene available from Kuraray as SEPTON S8104; Polystyrene-poly (ethylene-ethylene / propylene) -polystyrene triblock copolymers available from Kuraray as SEPTON S4044, S4055, S4077, and S4099; And a polystyrene-poly (ethylene-propylene) -polystyrene triblock copolymer containing 65 wt% polystyrene available from Kuraray as SEPTON S2104. Mixtures of two or more hydrogenated block copolymers may also be used.

The composition comprises a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene in an amount of from 10 to 55% by weight, in particular from 20 to 50% by weight, more specifically from 25 to 45% by weight, %, More specifically 35 to 40 wt%.

In addition to the poly (arylene ether) -polysiloxane block copolymer reaction product and the hydrogenated block copolymer, the composition comprises a flame retardant. Suitable flame retardants include, for example, organophosphate esters, metal dialkyl phosphinates, nitrogen-containing flame retardants, metal hydroxides, metal borates, and mixtures thereof.

In addition to poly (arylene-ether) and block copolymers, the thermoplastic compositions include flame retardants. Suitable flame retardants include, for example, triaryl phosphates such as triphenyl phosphate, alkylated triphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis (di-2,6-xylyl phosphate) Melamine salts such as melamine cyanurate, melamine phosphate, melamine pyrophosphate, and melamine polyphosphate), metal phosphates (e.g., aluminum tris (diethylphosphinate) , Metal borates (e.g., zinc borate), metal hydroxides (e.g., magnesium hydroxide and aluminum hydroxide), and combinations thereof.

The thermoplastic composition may contain the flame retardant in an amount of 1 to 25 wt%, specifically 5 to 20 wt%, based on the total weight of the thermoplastic composition.

In some embodiments, the flame retardant comprises an organophosphate ester. Examples of organophosphate ester flame retardants include phenyl esters, phosphate esters comprising a substituted phenyl group or a combination of phenyl groups and substituted phenyl groups, bis-aryl phosphate esters based on resorcinol, such as resorcinol bis-di Phenyl phosphate, and those based on bisphenol, such as bisphenol A bis-diphenyl phosphate. In some embodiments, the organophosphate ester is selected from the group consisting of tris (alkylphenyl) phosphate (e.g., CAS No. 89492-23-9 or CAS No. 78-33-1), resorcinol bis (diphenylphosphate) (For example, CAS No. 57583-54-7), bisphenol A bis (diphenylphosphate) (for example, CAS No. 181028-79-5), triphenylphosphate (for example, CAS No. 115 -86-6), tris (isopropylphenyl) phosphate (e.g., CAS No. 68937-41-7), and mixtures of two or more of said organophosphate esters.

In some embodiments, the organophosphate ester comprises a bis-aryl phosphate having the structure:

In the formula, each R independently represents a C ₁ -C ₁₂ alkylidene group; R ^{16 and} R ¹⁷ are each independently a C ₁ -C ₅ alkyl group; R ¹² , R ¹³ , and R ¹⁵ are independently C ₁ -C ₁₂ hydrocarbyl; R ¹⁴ are each independently, C ₁ -C ₁₂ hydrocarbyl, and; m is an integer from 1 to 25; s1 and s2 are independently integers of 0, 1, or 2; In some embodiments, OR ⁵ , OR ⁶ , OR ⁷ , and OR ⁸ are independently derived from phenol, monoalkylphenol, dialkylphenol, or trialkylphenol.

As is readily understood by those skilled in the art, bis-aryl phosphate is derived from bisphenols. Examples of the bisphenol include 2,2-bis (4-hydroxyphenyl) propyne (so-called bisphenol A), 2,2-bis (4-hydroxy- Methane, bis (4-hydroxy-3,5-dimethylphenyl) methane, and 1,1-bis (4-hydroxyphenyl) ethane. In some embodiments, the bisphenol comprises bisphenol A.

In some embodiments, the flame retardant comprises a metal dialkyl phosphinate. As used herein, the term "metal dialkyl phosphinate" means a salt comprising at least one metal cation and at least one dialkyl phosphinate anion. In some embodiments, the metal dialkyl phosphinate is represented by the formula:

In the formula, R ¹¹ and R ¹² each independently represent C ₁ -C ₆ alkyl; M is calcium, magnesium, aluminum or zinc; d is 2 or 3; Examples of R ¹¹ and R ¹² include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, and cyclohexyl. In some embodiments, R ¹ and R ² are ethyl, M is aluminum, and d is 3 (ie, the metal dialkyl phosphinate is aluminum tris (diethylphosphinate)).

In some embodiments, the metal dialkyl phosphinate is in the form of particles. The metal dialkyl phosphinate may have a median particle diameter (D50) of less than or equal to 40 microns, or more specifically, a D50 of less than or equal to 30 microns, or, more specifically, a D50 of less than or equal to 25 microns. In addition, metal dialkyl phosphinates can be combined with polymers such as poly (arylene ether), polyolefins, polyamides, block copolymers, or combinations thereof to form the masterbatch. The metal dialkyl phosphinate masterbatch comprises metal dialkyl phosphinates in much greater amounts than are present throughout the composition. The use of masterbatches to add metal dialkyl phosphinates to other components of the composition facilitates the addition of metal dialkyl phosphinates and improves the distribution of metal dialkyl phosphinates.

In some embodiments, the flame retardant comprises a nitrogen-containing flame retardant comprising a nitrogen-containing heterocyclic base and a phosphate, a pyrophosphate, a conjugate acid of polyphosphate, or a cyanurate base. In embodiments where the conjugated acid is a phosphate, pyrophosphate, or polyphosphate, the nitrogen-containing flame retardant is represented by the formula:

G is from 1 to about 10,000 and the ratio of f: g is from about 0.5: 1 to about 1.7: 1, specifically from 0.7: 1 to 1.3: 1, more specifically from 0.9: 1 to 1.1: 1. It will be understood that this formula includes species in which one or more protons have been transferred from the polyphosphate group to the melamine group (s). When g is 1, the nitrogen-containing flame retardant is melamine phosphate (CAS Registry No. 20208-95-1). When g is 2, the nitrogen-containing flame retardant is melamine pyrophosphate (CAS registry number 15541-60-3). When g is greater than 2 on average, the nitrogen-containing flame retardant is melamine polyphosphate (CAS Registry Number 56386-64-2). In some embodiments, the nitrogen-containing flame retardant is melamine pyrophosphate, melamine polyphosphate, or a mixture thereof. In embodiments wherein the nitrogen-containing flame retardant is melamine polyphosphate, g has an average value of greater than 2 and less than or equal to about 10,000, specifically, from about 5 to about 1,000, and more specifically, from about 10 to about 500. In embodiments wherein the nitrogen-containing flame retardant is a melamine polyphosphate, g has an average value of greater than 2 and less than or equal to about 500. Methods for preparing melamine phosphate, melamine pyrophosphate, and melamine polyphosphate are already known and are all commercially available. For example, melamine polyphosphate may be prepared by reacting polyphosphoric acid with melamine, as described in U.S. Patent No. 6,025,419 (inventor: Kasowski et al.), Or by reacting with melamine in accordance with International Patent Publication WO 98/08898 A1 (inventor: Jacobson et al. ), By heating melamine pyrophosphate at 290 占 폚 under a nitrogen atmosphere until the weight becomes constant. In some embodiments, the nitrogen-containing flame retardant is melamine cyanurate (CAS registry number 37640-57-6).

The nitrogen-containing flame retardant may have low volatility relative to the temperature used to melt blend the composition. For example, in some embodiments, the nitrogen-containing flame retardant is heated to a temperature of from 25 ° C to 280 ° C, specifically from 25 ° C to 300 ° C, more specifically from 25 ° C to 320 ° C, at a rate of 20 ° C / ≪ / RTI > by thermal gravimetric analysis.

In some embodiments, the flame retardant comprises a metal hydroxide. Suitable metal hydroxides include all those that can provide flame retardancy and combinations thereof. The metal hydroxide may be chosen so that it does not substantially decompose upon the treatment of the combustion aid composition and / or the flame retardant thermoplastic composition. Here, substantially not decomposed is defined as a degree of decomposition that does not prevent the flame retardant additive composition from providing a level of fire suppression desired to be obtained. Examples of metal oxides include magnesium hydroxide (e.g., CAS No. 1309-42-8), aluminum hydroxide (e.g., CAS No. 21645-51-2), cobalt hydroxide (e.g., CAS No. 21041 -93-0), and combinations thereof. In some embodiments, the metal hydroxide comprises magnesium hydroxide. In some embodiments, the metal hydroxide has an average particle size of 10 mu m or less and / or a purity of 90 wt% or more. In some embodiments, it is preferred that the metal hydroxide is substantially free of water, that is, less than 1% by weight weight loss when dried at 120 < 0 > C for 1 hour. In some embodiments, metal hydroxides may be coated with, for example, stearic acid or other fatty acids.

In some embodiments, the flame retardant comprises a metal borate. Suitable metal borates include zinc borate, barium metaborate, magnesium borate, calcium borate, potassium tetraborate, sodium borate, and combinations thereof.

In some embodiments, the flame retardant is selected from the group consisting of metal dialkyl phosphinates, triaryl phosphates, metal hydroxides, metal borates, melamine cyanurates, and mixtures thereof.

In some embodiments, the flame retardant comprises a metal dialkyl phosphinate.

In some embodiments, the flame retardant comprises triaryl phosphate.

In some embodiments, the flame retardant comprises metal dialkyl phosphinates and triaryl phosphates.

The composition comprises 2 to 25 weight percent of a flame retardant, based on the weight of the composition. Within this range, the amount of the flame retardant may be 5 to 20% by weight, specifically 8 to 16% by weight. The specific amount of flame retardant may depend on factors including the flame retardant form, the total polyolefin content of the composition, and the intended use of the composition. When the flame retardant is mainly composed of a metal dialkyl phosphinate such as aluminum tris (diethylphosphate), the amount of the flame retardant is 3 to 16% by weight, specifically 5 to 12% by weight, more specifically 6 to 9% % ≪ / RTI > When the flame retardant is mainly composed of triarylphosphate such as resorcinol bis (diphenylphosphate) or bisphenol A bis (diphenylphosphate), the amount of the flame retardant may be 5 to 18% by weight, specifically 10 to 16% by weight have. When the flame retardant is mainly composed of a metal hydroxide, the total amount of the flame retardant may be 20 to 40% by weight, specifically 25 to 35% by weight. When the flame retardant is mainly composed of a metal borate salt, the total amount of the flame retardant may be 2 to 25% by weight, specifically 10 to 15% by weight.

In addition to the poly (arylene ether) -polysiloxane block copolymer reaction product, the hydrogenated block copolymer and the flame retardant, the composition may optionally further comprise a polyolefin.

The term "polyolefin" when used without the modifier "total" (as in "total polyolefin") refers to olefin homopolymers and copolymers. That is, the polyolefin is a polymerization product of monomers composed of aliphatic hydrocarbons unsaturated in an aliphatic form. Thus, the aromatic moieties are extruded from the polyolefin, as is the case with heteroatoms (i.e., atoms other than carbon and hydrogen). Examples of olefin homopolymers include polyethylene, high density polyethylene (HDPE), medium density polyethylene (MDPE), and isotactic polypropylene. Olefin copolymers may be prepared by copolymerizing ethylene and copolymers of ethylene and one or more poly (co-lyophilic diene) rubbers, as well as copolymers of alpha-olefins such as propene, 4-methyl-1-pentene, And propylene, and copolymers of one or more poly (co-lyophilic diene) rubbers. Also included are copolymers of ethylene and C ₃ -C ₁₀ monoolefins and copolymers of non-conjugated dienes, referred to herein as EPDM copolymers. Examples of C ₃ -C ₁₀ monoolefins for EPDM copolymers include propene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, and the like. Dienes include 1,4-hexadiene and monocyclic and polycyclic dienes. The molar ratio of ethylene: C ₃ -C ₁₀ monoolefins may range from 95: 5 to 5:95, and diene units may be present in amounts of from 0.1 to 10 mol%. The olefin copolymer further comprises linear low density polyethylene (LLDPE). The term "polyolefin" further includes a mineral oil.

The polyolefin, when present, may be used in an amount of 1 to 50 wt%, specifically 5 to 40 wt%, more specifically 10 to 35 wt%, based on the total weight of the composition. In some embodiments, the composition comprises 3 to 15 weight percent polybutene. In some embodiments, the composition comprises 3-15 wt% polypropylene.

When it is desired to obtain a high flame retardancy, it is helpful to limit the total polyolefin content of the composition. As used herein, the term "total polyolefin" includes polyolefins as defined above, as well as polyolefin segments of block and graft copolymers. For example, the total polyolefin may be a poly (ethylene-butylene) segment of a polystyrene-poly (ethylene-butylene) -polystyrene block copolymer, and a poly (ethylene- ) Segments. As another example, the total polyolefin comprises the poly (ethylene-octene) backbone of a poly (ethylene-octene) -graft-poly (maleic anhydride) graft copolymer. Since the "total polyolefin" contains only aliphatic content, the poly (alphenyl aromatic) content is excluded. In some embodiments, the composition comprises up to 55% by weight total polyolefin, based on the total weight of the composition.

The composition may be specified not only in terms of the weight percentage of each component but also in terms of the weight ratio of the components. Thus, in some embodiments, the weight ratio of total polyolefin to poly (arylene ether) -polysiloxane block copolymer reaction product is 1.5: 1 or less, specifically 0.3: 1 to 1.5: 1, more specifically 0.5: 1.3: 1, more specifically from 0.8: 1 to 1.2: 1, wherein the total polyolefin consists of a polyolefin, a polyolefin block in the block copolymer, and a polyolefin skeleton and graft in the graft copolymer.

The composition may be specified in terms of the ratio of the total polyolefin to the sum of the poly (arylene ether) -polysiloxane block copolymer reaction product and the flame retardant. Thus, in some embodiments, the total weight ratio of total polyolefin to flame retardant to poly (arylene ether) -polysiloxane block copolymer reaction product is 1.2: 1 or less, specifically 0.5: 1 to 1.1: 1, 0.6: 1 to 0.9: 1, wherein the total polyolefin consists of a polyolefin, a polyolefin block in the block copolymer, and a polyolefin skeleton and graft in the graft copolymer.

The composition may be specified in terms of the ratio of polyolefin to the sum of the poly (arylene ether) -polysiloxane block copolymer reaction product and the flame retardant. In this connection, "polyolefin" is composed of an olefin homopolymer and a copolymer. Thus, in some embodiments, the total weight ratio of polyolefin to flame retardant to poly (arylene ether) -polysiloxane block copolymer reaction product is 1.1: 1 or less, specifically 0.1: 1 to 1: 1, more specifically 0.2 : 1 to 0.8: 1, more specifically 0.3: 1 to 0.6: 1.

The composition may optionally further comprise various additives known in the art of thermoplastics. For example, the composition may optionally comprise one or more additives selected from the group consisting of stabilizers, antioxidants, release agents, processing aids, drip retarders, nucleating agents, UV blocking agents, dyes, pigments, fragrances, antistatic agents, metal deflocculants, And the like, and combinations thereof. The additive, if present, is typically used in a total amount of about 0.5 to 10 wt%, based on the total weight of the composition.

Ingredients that are not required or are not shown as optional herein may optionally be excluded from the composition. For example, in some embodiments, the composition excludes any polymer except poly (arylene ether) -polysiloxane block copolymer reaction product, hydrogenated block copolymer, and optional polyolefin. In some embodiments, the poly (arylene ether) composition comprises a homopolymer of a polyamide, a polyester, an alkenyl aromatic monomer (e.g. homopolystyrene), poly (phenylene sulfide), hydrogenation of alkenyl aromatic and co- Unblocked block copolymer, and rubber-modified polystyrene.

In some embodiments, the composition excludes fillers. Exclusion of fillers does not exclude minor amounts (e. G., Less than 10% by weight) of mineral pigments, such as titanium dioxide, when used for pigmenting compositions. In some embodiments, the poly (arylene ether) composition does not include carbon black.

In a very specific embodiment, the composition comprises 25-42 wt% poly (arylene ether) -polysiloxane block copolymer reaction product; The poly (arylene ether) block comprises an arylene ether repeat unit having the structure:

The polysiloxane block has the structure:

N is from 35 to 60; The poly (arylene ether) -polysiloxane block copolymer reaction product has a number average molecular weight of 10,000 to 30,000 atomic mass units; Said composition comprising 25 to 45 wt% hydrogenated block copolymer; The hydrogenated block copolymer comprises a polystyrene-poly (ethylene-butylene-styrene) -polystyrene triblock copolymer and a polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer; Said composition comprising 6 to 16% by weight of a flame retardant; Wherein the flame retardant comprises triaryl phosphate; Wherein the composition comprises from 25 to 45% by weight of total polyolefin, wherein the total polyolefin consists of a polyolefin, a polyolefin block in the block copolymer, and a polyolefin skeleton and graft in the graft copolymer; The total ratio of polyolefin to flame retardant to poly (arylene ether) -polysiloxane block copolymer reaction product is from 0.55: 1 to 0.95: 1.

The composition may be formed by melt-kneading a poly (arylene ether) -polysiloxane block copolymer reaction product, a hydrogenated block copolymer, a flame retardant, and optional optional ingredients. Melting-kneading devices are known in the art and include similar mixing devices capable of applying shear forces to short- and twin-screw extruders and compositions. A specific melt-kneading process is described in the working examples below.

The composition exhibits improved flame retardancy over the corresponding composition where the poly (arylene ether) is substituted for the poly (arylene ether) -polysiloxane block copolymer reaction product. For example, in some implementations, the composition is tested in the UL 94 Vertical Burning Test, when run at a sample thickness of 6.4 mm, of less than or equal to 50 seconds, specifically less than or equal to 40 seconds, And an average flame out time of 30 seconds or less. As another example, in some embodiments, the composition is a single coated copper wire having an outer diameter of 2 mm, a core diameter of 0.6 mm, and a coating thickness of 0.7 mm in a UL 1581, Section 1080 (VW-1 Vertical Specimen) flammability test. , It indicates an average combustion stop time of 20 seconds or less, specifically 15 seconds or less.

The composition may also exhibit an improvement in one or more physical properties as compared to a corresponding composition wherein the poly (arylene ether) is substituted for the poly (arylene ether) -polysiloxane block copolymer reaction product. For example, in some embodiments, the composition exhibits a tensile elongation at break value of at least 100%, specifically at least 150%, at a value measured according to ASTM D638 at 23 ° C.

The present invention extends to articles formed from the composition. Thus, one embodiment includes a poly (arylene ether) -polysiloxane comprising a poly (arylene ether) homopolymer, and a poly (arylene ether) block and a polysiloxane block comprising an average of 35 to 80 siloxane repeat units 5 to 55% by weight of a poly (arylene ether) -polysiloxane block copolymer reaction product comprising a block copolymer; From 10 to 50% by weight of a hydrogenated block copolymer of a conjugated diene with an alkenyl aromatic compound; And 2 to 20% by weight of a flame retardant, wherein the poly (arylene ether) -polysiloxane block copolymer reaction product comprises 1 to 8% by weight of siloxane repeat units and 92 to 99% by weight of arylene ether repeat units Include; Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product is a product of a process comprising oxidizing a monomer mixture comprising a monovalent phenol and a hydroxyaryl-terminated polysiloxane in an oxidative manner; Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product has a weight average molecular weight of at least 30,000 atomic mass units, and wherein all of the weight percentages are based on the total weight of the composition. Lt; RTI ID = 0.0 > extruded < / RTI >

Other embodiments include a coated wire comprising a conductor and a covering disposed on the conductor, wherein the covering comprises the composition described above. For example, one embodiment is a coated conductor having a normal to large conductor cross-sectional area corresponding to AWG 5 to AWG 24. The thickness of the coating may be, for example, 0.25 to 8.0 mm. The coating comprises the compositions described herein. The conductor may be a single thread / strand or a bundle of multiple threads / strands. The conductor material may be a metal for power transmission or electronic signal transmission (e.g., copper, aluminum, steel, copper alloy, aluminum alloy, copper coated aluminum, nickel and / or tin coated copper). Wherein the coated conductor comprises a conductor and a covering comprising a thermoplastic composition and wherein the covering is disposed on the conductor, the conductor having a cross-section conforming to one or more of the following: (i) American wire gauge of AWG 24 to AWG 5 (AWG); (ii) the cross-sectional area of 0.20 to 16.8 mm2 (corresponding to AWG 24 to AWG 5 in accordance with ASTM B256-02); (Iii) nominal diameter of 0.51 to 4.62 mm (corresponding to AWG 24 to AWG 5 in accordance with UL 1581, 4th edition, Table 20.1). The covering of the coated conductor has a thickness of 0.25 to 8 mm.

Another embodiment is a small conductor with a thin coating. In this embodiment, the conductors have a cross-sectional area corresponding to AWG 26 to AWG 56. The thickness of the coating can be, for example, 0.010-0.85 mm. The coating comprises the compositions described herein. The conductor may be a single thread / strand or a bundle of multiple threads / strands. The conductor material may be a metal for power transmission or electronic signal transmission (e.g., copper, aluminum, steel, copper alloy, copper coated aluminum, nickel and / or tin coated copper). Another embodiment is an automotive wire harness assembly comprising a coated conductor and an end use product comprising the automotive wire harness assembly. The conductor material may also be glass or plastic used for optical fiber applications for signal transmission. The conductor has a cross-section that conforms to one or more of the following: (i) American Wire Gauge (AWG) from AWG 56 to AWG 26; (ii) the cross-sectional area of 0.000122-0.128 mm2 (corresponding to AWG 56 to AWG 26 in accordance with ASTM B256-02); (Iii) nominal diameter of 0.0124 to 0.404 mm (corresponding to AWG 56 to AWG 26 in accordance with UL 1581, fourth edition, Table 20.1). The covering of the coated conductor may have a thickness of 0.010-0.85 mm.

The present invention includes at least the following embodiments.

Example 1: Preparation of a poly (arylene ether) -polysiloxane block copolymer comprising a poly (arylene ether) homopolymer and a polysiloxane block comprising a poly (arylene ether) block and an average of 35 to 80 siloxane repeat units From 5 to 55% by weight of a poly (arylene ether) -polysiloxane block copolymer reaction product; 10 to 55% by weight hydrogenated block copolymer of a conjugated diene with an alkenyl aromatic compound; And 2-25 wt% of a flame retardant, wherein the poly (arylene ether) -polysiloxane block copolymer reaction product comprises 1-8 wt% siloxane repeat units and 92-99 wt% arylene ether repeat units Include; Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product is a product of a process comprising oxidizing a monomer mixture comprising a monovalent phenol and a hydroxyaryl-terminated polysiloxane in an oxidative manner; Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product has a weight average molecular weight of at least 30,000 atomic mass units, all of the weight percentages being based on the total weight of the composition.

Embodiment 2: The composition of embodiment 1, wherein said poly (arylene ether) -polysiloxane block copolymer reaction product has a weight average molecular weight of from 30,000 to 150,000 atomic mass units.

Embodiment 3: The composition according to embodiment 1 or 2, wherein the poly (arylene ether) -polysiloxane block copolymer reaction product has an intrinsic viscosity of 0.3 to 0.6 dl / g, as measured in chloroform at 25 캜.

Embodiment 4: In any one of embodiments 1-3, the poly (arylene ether) -polysiloxane block copolymer reaction product comprises a molecule having a molecular weight of less than 10,000 atomic mass units in an amount less than 25% by weight , Composition.

Embodiment 5: The composition of embodiment 4, wherein the molecule having a molecular weight of less than 10,000 atomic mass units comprises an average of 5 to 10 weight% of siloxane repeat units.

Embodiment 6: The composition of any of embodiments 1-5, wherein the poly (arylene ether) -polysiloxane block copolymer reaction product comprises 25 wt% of molecules having a molecular weight greater than 100,000 atomic mass units.

Embodiment 7: The composition of embodiment 6, wherein said molecule having a molecular weight greater than 100,000 atomic mass units comprises an average of 3-6% siloxane repeat units.

Embodiment 8: The membrane according to any one of embodiments 1 to 7, wherein the monovalent phenol is composed of 2,6-dimethylphenol and the poly (arylene ether) -polysiloxane block copolymer reaction product is not more than 0.4% A 2,6-dimethylphenoxy group.

Embodiment 9: A method as in any one of embodiments 1-8, wherein the monohydric phenol is composed of 2,6-dimethylphenol and the poly (arylene ether) -polysiloxane block copolymer reaction product is less than 1% A 2,6-dimethylphenoxy group.

Embodiment 10: In embodiments 10 to 9, the poly (arylene ether) block comprises an arylene ether repeat unit having the structure:

Wherein in each repeating unit, each Z ¹ is independently halogen, Beach cyclic or substitutional C ₁ -C ₁₂ hydrocarbyl, with the proviso that the hydrocarbyl group is not a tertiary hydrocarbyl, C ₁ - C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbyloxy, or C ₂ -C ₁₂ halo hydrocarbyloxy, wherein two or more carbon atoms separate hydrogen and oxygen atoms; Each Z ² is independently hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl, provided that the hydrocarbyl group is not a tertiary hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbyloxy, or C ₂ -C ₁₂ halo hydrocarbyloxy, wherein two or more carbon atoms separate hydrogen and oxygen atoms; Said polysiloxane block comprising repeating units having the structure:

Wherein each R ¹ and R ² is independently hydrogen, C ₁ -C ₁₂ hydrocarbyl or C ₁ -C ₁₂ halo hydrocarbyl; Wherein the polysiloxane block further comprises a termination unit having the structure:

Formula, Y is hydrogen, C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbyl-oxy, or halogen, each of R ³ and R ⁴ are independently hydrogen, C ₁ -C ₁₂ hydrocarbyl Or C ₁ -C ₁₂ halohydrocarbyl.

Embodiment 11: In any one of Embodiments 1 to 10, the poly (arylene ether) block comprises an arylene ether repeating unit having the structure:

Said polysiloxane block having the structure:

N is from 35 to 60; Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product has a number average molecular weight of 10,000 to 30,000 atomic mass units.

Embodiment 12: The membrane according to any one of embodiments 1-11, wherein the total polyolefin comprises at most 55% by weight, based on the total weight of the composition, of polyolefin, polyolefin block in the block copolymer, and graft copolymer ≪ / RTI > wherein the composition comprises a polyolefin skeleton and a graft.

Embodiment 13: The method of any one of embodiments 1-12, wherein the weight ratio of the total polyolefin to the poly (arylene ether) -polysiloxane block copolymer reaction product is 1.5: 1 or less; Wherein the total polyolefin consists of a polyolefin, a polyolefin block in the block copolymer, and a polyolefin skeleton and graft in the graft copolymer.

Embodiment 14: The process of any one of embodiments 1-13, wherein the total weight ratio of the total polyolefin to the reaction product of the flame retardant and the poly (arylene ether) -polysiloxane block copolymer is 1.2: 1 or less; Wherein the total polyolefin consists of a polyolefin, a polyolefin block in the block copolymer, and a polyolefin skeleton and graft in the graft copolymer.

Embodiment 15: The method of any one of embodiments 1-14, wherein the total weight ratio of the total polyolefin to the reaction product of the flame retardant and the poly (arylene ether) -polysiloxane block copolymer is 1: 1 or less; Wherein the polyolefin is comprised of an olefin homopolymer and a copolymer.

[0063] Embodiment 16: The composition of any one of embodiments 1-15, wherein the hydrogenated block copolymer comprises a polystyrene-poly (ethylene-butylene-styrene) -polystyrene triblock copolymer.

Embodiment 17: The method of any one of embodiments 1-16 wherein the hydrogenated block copolymer is selected from the group consisting of polystyrene-poly (ethylene-butylene-styrene) -polystyrene triblock copolymer and polystyrene-poly (ethylene-butylene) - polystyrene triblock copolymer.

Embodiment 18: The composition of any one of embodiments 1-17, wherein the flame retardant is selected from the group consisting of metal dialkyl phosphinates, triaryl phosphate metal hydroxides, metal borates, melamine salts, and mixtures thereof.

[0051] Embodiment 19: The composition of any one of embodiments 1-18, wherein the flame retardant comprises a metal dialkyl phosphinate.

[0063] Embodiment 20: The composition of any one of embodiments 1-19, wherein the flame retardant comprises triaryl phosphate.

[0051] Embodiment 21: The composition of any of embodiments 1-20, wherein the flame retardant comprises a metal dialkyl phosphinate and a triaryl phosphate.

[0213] Embodiment 22: The composition of any one of embodiments 1-21, further comprising 1-50% by weight of a polyolefin.

Embodiment 23: The method of embodiment 1 wherein said composition comprises 25-42% by weight of said poly (arylene ether) -polysiloxane block copolymer reaction product; Wherein the poly (arylene ether) block comprises an arylene ether repeat unit having the structure:

Wherein said polysiloxane block has the structure:

N is from 35 to 60;

Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product has a number average molecular weight of from 10,000 to 30,000 atomic mass units; Said composition comprising 20 to 45 weight percent of said hydrogenated block copolymer; Wherein the hydrogenated block copolymer comprises a polystyrene-poly (ethylene-butylene-styrene) -polystyrene triblock copolymer and a polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer; Said composition comprising 6 to 16% by weight of said flame retardant; Wherein the flame retardant comprises triaryl phosphate; Said composition comprising from 25 to 45% by weight of total polyolefin; Wherein the total polyolefin consists of a polyolefin, a polyolefin block in the block copolymer, and a polyolefin skeleton and graft in the graft copolymer; Wherein the total ratio of said total polyolefin to said flame retardant and said poly (arylene ether) -polysiloxane block copolymer reaction product is from 0.6: 1 to 0.9: 1.

Embodiment 24: The composition of embodiment 23 further comprising 3 to 15 weight percent polybutene.

Embodiment 25: The composition of embodiment 23 further comprising 3-15% by weight polypropylene.

Example 26: A poly (arylene ether) -polysiloxane block copolymer comprising a polysiloxane block comprising a poly (arylene ether) homopolymer and a poly (arylene ether) block and an average of 35 to 80 siloxane repeat units From 5 to 55% by weight of a poly (arylene ether) -polysiloxane block copolymer reaction product; From 10 to 50% by weight of a hydrogenated block copolymer of a conjugated diene with an alkenyl aromatic compound; And 2 to 20% by weight of a flame retardant, wherein the poly (arylene ether) -polysiloxane block copolymer reaction product comprises 1 to 8% by weight of siloxane repeat units and 92 to 99% by weight of arylene ether repeat units Include; Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product is a product of a process comprising oxidizing a monomer mixture comprising a monovalent phenol and a hydroxyaryl-terminated polysiloxane in an oxidative manner; Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product has a weight average molecular weight of at least 30,000 atomic mass units, and wherein all of the weight percentages are based on the total weight of the composition. An extruded or injection molded article comprising a product.

Embodiment 27: The article of embodiment 26 wherein the extruded or injection molded article comprises a coated wire comprising a conductor and a covering disposed on the conductor; Wherein the covering comprises the composition.

The present invention will be described more specifically by the following non-limiting examples.

Manufacturing example  1 to 6

These examples carried out on a pilot plant scale illustrate the effect of various process parameters on the product properties of the reaction products.

The process variables are summarized in Table 1, where "toluene source" is the freshly supplied toluene solvent ("new" in Table 1) or regenerated from poly (arylene ether) homopolymer synthesis Playback ");"DMBA level (%)" is the concentration of dimethyl-n-butylamine expressed in weight percent relative to the weight of toluene; "Solid (%)" is the total weight of 2,6-dimethylphenol and eugenol-capped polysiloxane expressed as% by weight based on the total weight of 2,6-dimethylphenol, the eugenol-capped polysiloxane and toluene; "Polysiloxane chain length" is the average number of dimethylsiloxane (-Si (CH ₃ ) ₂ O-) units in the eugenol-capped polysiloxane; "Polysiloxane load (%)" is the weight percent of the yuanole-capped polysiloxane in the reaction mixture, based on the total weight of the eugenol-capped polysiloxane and 2,6-dimethylphenol; "Initial 2,6-dimethylphenol (%)" means the weight of 2,6-dimethylphenol present in the reaction vessel at the initial stage of polymerization (the step of introducing oxygen into the reaction vessel) %ego; The "O: 2,6-dimethylphenol molar ratio" is the molar ratio of 2,6-dimethylphenol maintained at the addition of oxygen in the atomic state (provided as oxygen molecule) to 2,6-dimethylphenol; "Temperature, initial charge (DEG C)" is the temperature (unit: DEG C) of the reaction mixture when the initial charge of the monomer is added to the reaction vessel and when oxygen is initially introduced into the reaction mixture; "Temperature, addition (DEG C)" is the reaction temperature during the addition of 2,6-dimethylphenol; "Temperature, build (° C)" is the temperature (expressed in ° C) during the build phase of the reaction; "Ramp time (minutes)" is the time (expressed in minutes) at which the temperature rises from the addition temperature to the build temperature; "Ramp slope (° C / min)" is the rate of change of temperature (expressed in degrees Celsius / min) while the temperature rises from the addition temperature to the build temperature; The "temperature rise time (min)" is the total reaction time (expressed in minutes) elapsed between the introduction of oxygen and the stop of oxygen. For all variables, the controlled monomer addition time is 40-80 minutes from the start of the reaction (i.e., initiation of the oxygen flow). The build time is measured from the end of the controlled monomer addition to the end of the reaction (i.e., the end of the oxygen flow); The build time varied between 80 and 160 minutes.

Process variables were superimposed in the general synthesis process as follows. The reaction was purged with nitrogen to obtain an oxygen concentration of less than 1%. Initial toluene (fresh or regenerated) was injected into the reactor, and the toluene was stirred at 500 rpm. The initial toluene temperature was adjusted to the "initial charge" temperature specified in Table 1 and maintained at that temperature during the addition of the initial charge of 2,6-dimethylphenol from the addition tank to the reaction vessel. After the addition of the initial charge of 2,6-dimethylphenol was completed, yuanol-capped polydimethylsiloxane, di-n-butylamine, dimethyl-n-butylamine, diamine, and copper catalysts were added to the reaction vessel . An oxygen flow and additional monomer addition were initiated and the oxygen flow was adjusted so that the concentration of head space was maintained at less than 17%. Upon addition of the additional monomer, the cooling water feed temperature was adjusted to maintain the temperature specified in Table 1 as "Temperature, addition (C) ". After monomer addition was complete, the monomer addition line was flushed with toluene and the reaction temperature was raised to the temperature specified in Table 1, "Temperature, build (C) ". This temperature control was carried out at a rate specified as "temperature rise slope (占 폚 / min) " over the time specified in Table 1 as" temperature rise time (min) ". The reaction was continued until the set point was reached. The set endpoint is the time at which the intrinsic viscosity and maximum siloxane incorporation is achieved, typically 80 to 160 minutes after the end of the 2,6-dimethylphenyl addition. When this point was reached, the oxygen flow was stopped. The reaction mixture was then heated to 60 DEG C and pumped into a chelation tank containing an aqueous chelating agent solution. The resulting mixture was stirred and held at 69 DEG C for 1 hour. The hard (organic) phase and the heavy (aqueous) phase were separated by decantation and the heavy phase was discarded. A small portion of the hard phase was sampled and precipitated as isopropanol for analysis and the remainder of the hard phase was pumped into the precipitation tank to remove the methanol anti-solvent (isopropanol anti-solvent ). The precipitate was filtered to form a wet cake, which was reslurried three times with the same anti-solvent and dried under a nitrogen atmosphere until a toluene concentration of less than 1 wt% was obtained.

The reaction conditions and the properties of the resulting product are summarized in Table 1. "Total volatile matter (%) ", which is the weight percent of volatile matter in the separated products, was determined by measuring the percent weight loss when dried for 1 hour at 110 캜 under vacuum. "Residual Cu (ppm)" which is the residual catalyst concentration expressed in ppm by weight of elemental copper was determined by atomic absorption spectroscopy; For properties as a function of reaction time, the sample was taken out of the reactor and precipitated by adding 1 volume of the reaction mixture to 3 volumes of room temperature isopropanol to give a precipitate which was filtered, washed with isopropanol, dried and then analyzed by ¹ H NMR Weight% and siloxane incorporation efficiency) and intrinsic viscosity analysis.

The number average molecular weight and the weight average molecular weight were determined by gel permeation chromatography as follows. The gel permeation chromatograph is calibrated using eight polystyrene standards each having a narrow molecular weight distribution and a collectively measured molecular weight range of 3,000 to 1,000,000 g / mole. The column used was le3 and le5A PLgel columns with 5 [mu] l 100 [mu] g PLgel guard column. Chromatography was performed at 25 < 0 > C. The eluent was chloroform containing 100 wt ppm of di-n-butylamine. The eluent liquid flow rate was 1.2 ml / min. The detector wavelength was 254 nm. The third order polynomial is fitted through the calibration point. The experimental sample is prepared by dissolving 0.27 g of the separated block copolymer solids in 45 ml of toluene. A 50 μl sample of the resulting solution is injected into the chromatograph. Number of values in the average molecular weight (M _n) and weight average molecular weight (M _w) is calculated from the measured signal using the polystyrene calibration line. The values are then equation using M (PPE) = 0.3122 × M (PS) 1.073, is converted to poly (2,6-dimethyl-1,4-phenylene ether) molecular weight of the polystyrene from the molecular weight, the formula M (PPE ) Is the molecular weight of poly (2,6-dimethyl-1,4-phenylene ether) and M (PS) is the molecular weight of polystyrene.

The reaction conditions and the properties of the resulting product are summarized in Table 1. &Quot; Molecular weight < 10 K (%) "is the weight percent of the separated reaction product having a molecular weight of less than 10,000 atomic mass units, as determined by gel permeation chromatography, in the properties of the product in Table 1; "Molecular Weight> 100 K (%)" is the weight percent of the separated reaction product having a molecular weight of less than 10,000 atomic mass units, as determined by gel permeation chromatography; "IV, end of reaction (dL / g)" is the intrinsic viscosity (in deciliters per gram) of the dry powder separated by precipitation from isopropanol, measured by a Ubbelohde viscometer at 25 ° C in chloroform; "IV, termination of the chelation (dL / g)" refers to the intrinsic viscosity, measured by a Ubbelohde viscometer at 25 ° C in chloroform, of the product present in the organic phase after drying that has been separated by precipitation from isopropanol, Is deciliter per gram); The term "M _w , termination of reaction (AMU)" means the weight average molecular weight of the product, which is separated by precipitation from isopropanol and dried, and which is present in the reaction mixture at the end of the polymerization reaction and measured by gel permeation chromatography Atomic mass unit); The term " M _n , termination of reaction (AMU) "means the number average molecular weight of the product, which is separated by precipitation from isopropanol and dried, and which is present in the reaction mixture at the end of the polymerization reaction and measured by gel permeation chromatography Atomic mass unit); "M _w / M _n , termination of the reaction" is the ratio of the weight average molecular weight to the number average molecular weight of the product which is separated by precipitation from isopropanol and then dried, at the end of the polymerization, of the product present in the reaction mixture; The term "M _w , end of chelation (AMU)" refers to the product of a product present in the organic phase after drying that has been separated by precipitation from isopropanol, dried, and has a weight average molecular weight )ego; The term " M _n , end of chelation (AMU) "refers to the number average molecular weight (unit is mass per unit mass) measured by gel permeation chromatography of a product present in the organic phase after drying, separated by precipitation from isopropanol, )ego; The term " M _w / M _n , termination of the chelation "is the ratio of the weight average molecular weight to the number average molecular weight of the product present in the organic phase after drying, which is separated by precipitation from isopropanol and dried.

In Table 1, "siloxane weight% (%)" is the weight percent of dimethylsiloxane units based on the total weight of 2,6-dimethyl-1,4-phenylene ether units and dimethylsiloxane units in the isolated product, Is determined by < ¹ > H NMR using protons labeled a and b in the structure labeled "formula (I) "

here,

In the formula for X, "Mn siloxane fluid" is the number average molecular weight of the dimethylsiloxane units in the hydroxyaryl-terminated polysiloxane, and "MW 2,6 xylenol" in the formula for Y is the molecular weight of 2,6- to be. Calling this metric "siloxane wt%" is an oversimplification in that it disregards the separated product components, except 2,6-dimethyl-1,4-phenylene ether units and dimethylsiloxane units. Nevertheless, this is a useful metric.

In Table 1, the "siloxane incorporation efficiency (%)" is calculated by comparing the total monomer composition (unreacted (unincorporated) siloxane macromer removed from the precipitate from isopropanol) to the weight percent of dimethylsiloxane units used in the reaction mixture Is determined by ¹ H NMR using the protons labeled a and b in the structure labeled "Formula (I) ", and calculated as the weight% of dimethylsiloxane units in the separated product,

Here, the formula for the weight% of siloxane in the product is given in advance,

Wherein the weight of the loaded siloxane monomer is the weight of the hydroxyaryl-terminated polysiloxane used in the reaction mixture and "the weight of the loaded 2,6-monomer" is the weight of the 2,6-dimethylphenol used in the reaction mixture Quot; siloxane incorporation efficiency "is an oversimplification in that it ignores the possibility that small amounts of monomers and oligomers may be lost during the separation process. For example, all hydroxyaryl-terminated polysiloxanes It is theoretically possible for siloxane incorporation efficiency to exceed 100% if incorporated into the block copolymer and part of the arylene ether oligomer is lost during the separation process. However, the siloxane incorporation efficiency is a useful metric.

In Table 1, "tail (%)" means the percentage of 2,6-dimethylphenol having an end group structure as compared to all 2,6-dimethylphenol residues, Gt; ¹ < / RTI > NMR using a proton labeled with < RTI ID = 0.0 >

Here, the expression for Y

In Table 2, "biphenyl (%)" is the weight percent of 3,3 ', 5,5'-tetramethyl-4,4'-biphenol residue,

As determined by ¹ H NMR using a "biphenyl" proton labeled with d in the structure labeled "formula (II)" and a proton labeled with a in the structure labeled "formula (I)", Lt; / RTI >

Here, the expression for Y is given before,

Here, "MW biphenyl" is the molecular weight of the residue of the 3,3 ', 5,5'-tetramethyl-4,4'-biphenyl presented above.

"OH (ppm)" is on, after a derivatization of the hydroxyl groups of the separated sample ³¹ P NMR as described in to one and ppm by weight of all hydroxyl groups, based on the total weight of the separated sample literature is determined by:. KP Chan et al, " Facile Quantitative Analysis of Hydroxyl End Groups of Poly (2,6-dimethyl-1,4-phenylene oxide) s by 31 P NMR Spectroscopy", Macromolecules, volume 27, pages 6371- 6376 (1994).

Example 4 In order to characterize the composition as a function of the molecular weight fraction, fractions were collected from six gel permeation chromatography injections (36 mg in total injected material) using a Gilson fraction collector. The eluent spilled between run times 12 and 25 minutes was split into 60 test tubes which were later recombined to produce six fractions each containing approximately 16.67% total material (determined as an area percent of chromatogram). A small amount (200 μl) of the five fractions was analyzed by gel permeation chromatography to confirm that the fractionation was successful. The remainder was used for ¹ H NMR analysis. The portion used for NMR analysis was evaporated to dryness at 50 < 0 > C under a stream of nitrogen. 1 ml of deuterated chloroform (using tetramethylsilane as an internal standard) was added and the sample was analyzed by ¹ H NMR. The results presented in Table 4 indicate first that all fractions contain a substantial dimethylsiloxane content. The fact that no "% tail" was detected in the highest molecular weight fraction indicates that this fraction is essentially free of poly (arylene ether) homopolymer; This is essentially an inherently pure block copolymer. Likewise, the fact that the largest "% tail" is observed in the lowest molecular weight fraction means that the poly (arylene ether) is biased in a relatively low molecular weight fraction direction.

 Sample Description Siloxane weight
(%) Biphenyl weight
(%) Gross weight
(%)  Ratio -01 (83-100% of MW curve; highest Mw ratio) 4.39 0.56 0.00  Ratio -02 (67-83% of the MW curve) 4.18 0.85 0.00  Ratio -03 (50-83% of the MW curve) 4.34 0.87 0.00  Ratio -04 (33-50% of the MW curve) 4.71 1.16 0.09  Ratio -05 (17-33% of the MW curve) 5.27 1.61 0.19  Ratio -06 (0-17% of MW curve; lowest Mw ratio) 6.90 3.40 1.00

Examples 1 to 7 and Comparative Examples 1 to 9

These examples illustrate that improved properties were obtained by substituting the poly (arylene ether) -polysiloxane block copolymer reaction product for the poly (arylene ether) in the composition to be used as wire and cable insulation. Specifically, these examples illustrate the use of metal dialkyl phosphinate flame retardants.

Sixteen compositions were prepared using the ingredients listed in Table 3.

Specific compositions are described in detail in Table 6, where the amount of ingredients is expressed in parts by weight, except where stated in weight percent, and the weight percent value, if specified in weight percent, is based on the total weight of the composition. In Table 6, "total (pbw)" is the total weight of all components; (%) "Is the calculated weight percent of the hydrogenated block copolymer, based on the total weight of the composition (e.g., in the composition of Table 6, the hydrogenated block copolymer is SEBS IV, SEBS II , SEBS and SEPS contents of SEBS I and TPE); "Total PO (%)" is the calculated weight percent of total polyolefin, based on the total weight of the composition (e.g., for the composition of Table 6, the total polyolefin is POE, PP, mineral oil, polybutene, and all Poly (ethylene-butylene) content of SEBS material, poly (ethylene-butylene) content of SEBS in TPE component and poly (ethylene-propylene content) of SEPS in TPE component; "(total PO) / PPE Quot; is the weight / weight ratio of total polyolefin to poly (arylene ether), wherein the term "poly (arylene ether)" refers to poly (arylene ether) homopolymer as well as poly (arylene ether) "(Total PO) / (PPE + FR)" includes the poly (arylene ether) block and the polysiloxane block content of the total polyolefin (For example, in Table 6, "flame retardant" is composed of "DEPAL "; (Arylene ether) block of a poly (arylene ether) -polysiloxane block copolymer as well as a poly (arylene ether) homopolymer as well as a polysiloxane block content; "poly (arylene ether) Is the weight / weight ratio of the "polyolefin" to the sum of the poly (arylene ether) and the flame retardant, where "polyolefin" refers to the ratio of monomers composed of homopolymers and olefins The term "poly (arylene ether)" is intended to include poly (arylene ether), poly (arylene ether), and poly (arylene ether) ) Homopolymers as well as poly (arylene ether) blocks and polysiloxane block contents of poly (arylene ether) -polysiloxane block copolymers. In the following table, " SIA " Aminoethylaminopropylpolysiloxanes are included as flame retardants, such as citric acid monohydrate, which is listed as "CA ".

The compositions were compounded in a Toshiba Model TEM-37BS twin-screw extruder. The compounding conditions are summarized in Table 4.

Compounding parameter unit value die mm 4-10 Supply (Zone 0) Temperature ℃ 20-50 Zone 1 temperature ℃ 50-100 Zone 2 temperature ℃ 140-220 Zone 3 temperature ℃ 180-265 Zone 4 Temperature ℃ 205-285 Zone 5 temperature ℃ 205-285 Zone 6 Temperature ℃ 205-285 Zone 7 Temperature ℃ 205-285 Zone 8 Temperature ℃ 205-285 Zone 9 Temperature ℃ 205-285 Zone 10 Temperature ℃ 205-285 Zone 11 Temperature ℃ 205-285 Die temperature ℃ 215-285 Melt temperature ℃ 215-285 Screw speed rpm 300-500 Throughput kg / hr 20-50 talk % 20-80 Vacuum 1 MPa <0.08 Side feeder 1 speed rpm 200-300

The "material properties" listed in Table 6 were determined as follows. The test articles were injection molded using a barrel temperature of 250 ° C and a mold temperature of 40-60 ° C. The values of the melt flow rates are expressed in units of g / 10 min in Table 6 and expressed as "MFR, 250 DEG C, 10 kg (g / 10 min) ", and ASTM D1238- 04c. The value of the flexural modulus is expressed in MPa and measured at 23 DEG C in accordance with ASTM D790-07e1. The values of the modulus of elasticity are expressed in units of MPa and are expressed in "Modulus of elasticity (MPa)" in Table 6, measured according to ASTM D638-08 at 23 ° C; Using the same procedure, tensile stress at break and tensile stress at break, expressed in MPa as "tensile stress (MPa)" in Table 6 and expressed as "tensile elongation The tensile elongation at break was determined. The value of Shore A hardness, shown as "Shore A Hardness" in Table 6, was measured according to ASTM D2240-05 at 23 ° C. FOT UL94V, 3.2 mm (sec) "for a sample thickness of 3.2 mm, and the combustion stop time indicated as" FOT UL94V, 6.4 mm (sec) "for a sample thickness of 6.4 mm UL 94 Vertical Burning Flame Test.

In a material property value, a comparative example containing a homopolymer of poly (arylene ether) and a corresponding embodiment of the present invention containing a poly (arylene ether) -polysiloxane block copolymer reaction product are paired- wise), it shows improved tensile elongation and flame retardancy in the examples of the present invention. Concretely, regarding the tensile elongation, Comparative Example 1 showed a value of 157% in Example 1, compared to a value of 127%; Comparative Example 3 showed a value of 181% in Example 2, compared with a value of 109%; Comparative Example 5 showed a value of 166% in Example 3 compared to a value of 134%; Comparative Example 6 showed a value of 179% in Example 5 compared to a value of 123%; Comparative Example 8 showed a value of 177% in Example 6 compared to a value of 165%; Comparative Example 9 showed a value of 180% in Example 7, while it showed a value of 176%. Regarding the UL94 vertical combustion flame downtime determined at a sample thickness of 6.4 mm, Comparative Example 1 exhibited an average value of 11.54 seconds in Example 1 compared to an average value of 97.4 seconds; Comparative Example 3 showed an average value of 5.42 seconds in Example 2, while it showed an average value of 11.42 seconds; Comparative Example 5 showed an average value of 6.4 seconds in Example 3, while it showed an average value of 14.4 seconds; Comparative Example 6 showed an average value of 8.8 seconds in Example 5 compared to an average value of 23.3 seconds; Comparative Example 9 showed an average value of 53.9 seconds, whereas Example 7 showed an average value of 33.6 seconds. The comparison of the only pairwise method which did not show the flame retardancy advantage in the sample of the present invention was Example 6 showing an average value of 16.1 seconds compared to Comparative Example 8 which showed an average value of 12.8 seconds. In Table 6, in the FOT UL94V column, "F" means failure to achieve V-0, V-1 or V-2 rating in the UL94 vertical combustion test.

"Wire properties" in Table 6 were determined as follows. A test sample coated with a 0.6 mm diameter copper wire core (i.e., American Wire Gauge (AWG) 24 strand of 11 copper wires each having a diameter of 0.16 mm) and an outer diameter of 2 mm, Multi-stranded copper wire was produced using the extrusion coating parameters shown in Table 5. The combustion stop time "VW-1, 2C / FOT (second)" and "VW-1, 1C / FOT (second)" were measured in accordance with UL 1581, Section 1080 (VW-1 Vertical Specimen) Correspond to two coated wires that are held together side by side, and "1C " corresponds to a single coated wire. (%) "In Table 6, expressed in units of MPa and expressed as" tensile stress (MPa) "in Table 6, Elongation was measured at 23 캜 according to UL1581, Section 470. And the thermal deformation, expressed as "thermal deformation, 121 ° C., 250 g, 1 h" in Table 6, was measured at 121 ° C. and 250 g load according to UL 1581, Section 560 ("Deformation"

Comparing the comparative example containing the poly (arylene ether) homopolymer and the corresponding embodiment of the present invention containing the poly (arylene ether) -polysiloxane block copolymer, in terms of wire property values, Exhibit improved flame retardancy and tensile elongation in the examples of the present invention (generally those with a high level of flame retardancy). Specifically, with respect to the VW-1 1C average combustion stop time value, Comparative Example 3 showed a value of 15.0 seconds, whereas Example 2 showed a value of 7.7 seconds; Comparative Example 5 showed a value of 12.7 seconds in Example 3 as compared to that in which the test was unsuccessful; Comparative Example 6 failed the VW-1 2C test, whereas Example 5 showed a value of 21.7 seconds; Comparative Example 8 showed a value of 10.0 seconds in Example 6, compared with that of the VW-1 1C test. Regarding the tensile elongation value, Comparative Example 1 exhibited a value of 239% in Example 1, compared with 233%; Comparative Example 3 showed a value of 237% in Example 2 as compared with a value of 182%; Comparative Example 5 showed a value of 234% in Example 3, compared to a value of 205%; Comparative Example 6 showed a value of 254% in Example 5 compared to a value of 184%; Comparative Example 8 showed a value of 252% in Example 6 compared to a value of 218%; Comparative Example 9 had a value of 218%, whereas Example 7 had a value of 232%.

Wire coating extrusion parameters Typical Value unit Drying temperature 60-85 ℃ Drying time 8-12 time Maximum moisture content 0.02 % Extrusion length / diameter ratio (L / D) 22: 1 to 26: 1 - Screw extrusion ratio 1.2-3.5 - Screw speed 15-85 rpm Supply zone temperature 150-250 ℃ Intermediate zone temperature 220-270 ℃ Head zone temperature 220-280 ℃ Neck temperature 220-280 ℃ Cross-head temperature 220-280 ℃ Die temperature 220-280 ℃ Melt temperature 220-280 ℃ Conductor preheating temperature 25-150 ℃ Screen Pack 150-100 ㎛ Cooling water air gap 100-200 ㎛ Tank temperature 15-80 ℃

Examples 8 and 9, Comparative Examples 10 and 11

These examples illustrate that improved properties have been obtained by substituting poly (arylene ether) -polysiloxane block copolymer reaction products for poly (arylene ether) in compositions using metal dialkyl phosphinate flame retardants.

These examples illustrate the use of a flame retardant combination of triaryl phosphate and a metal dialkyl phosphinate.

The compositions were prepared and tested as described above. Composition and properties are summarized in Table 7.

Comparing the comparative example containing the poly (arylene ether) homopolymer and the corresponding embodiment of the present invention containing the poly (arylene ether) -polysiloxane block copolymer in terms of material properties, Lt; RTI ID = 0.0 &gt; tensile elongation &lt; / RTI &gt; and flame retardancy. Specifically, with respect to the tensile elongation, Comparative Example 10 showed a value of 49.6% in Example 8, compared with 38.2%; Comparative Example 11 showed a value of 98%, whereas Example 9 showed a value of 128%. Regarding the UL94 vertical combustion flame downtime determined at a sample thickness of 6.4 mm, Comparative Example 10 showed an average value of 37.4 seconds in Example 8 compared to an average value of 172.6 seconds; Comparative Example 11 showed an average value of 100.2 seconds, whereas Comparative Example 11 showed an average value of 10.6 seconds in Example 9. [

Comparing the comparative example containing the poly (arylene ether) homopolymer and the corresponding embodiment of the invention containing the poly (arylene ether) -polysiloxane block copolymer in wire property values, two Improved tensile elongation for both the samples of the present invention and improved VW-1 flame retardancy in one of the two inventive samples. Specifically, regarding the tensile elongation, Comparative Example 10 showed a value of 130% in Example 8, compared with a value of 117%; Comparative Example 11 showed a value of 170%, whereas Example 9 had a value of 187%. With respect to VW-1, 1C / FOT (sec), Comparative Example 10 failed the test (i.e., it exhibited a combustion stop time longer than 60 seconds and / or more than 25% ), And Example 8 showed an average combustion stop time of 13.3 seconds.

Comparative Example 10 Example 8 Comparative Example 11 Example 9 Furtherance PPE-46 35 0 30 0 PPE-Si 0 35 0 30 Polybutene 8 8 6 6 SEBS I 0 0 15 15 SEBS III 14 14 0 0 SEBS IV 7 7 0 0 PP 10 10 15 15 POE 10 10 18 18 DEPAL 3 3 6 6 BPADP 13 13 10 10 additive 1.6 1.6 1.6 1.6 Total (pbw) 101.6 101.6 101.6 101.6 Total HBC (%) 20.7 20.7 14.8 14.8 Total PO (%) 43.2 43.2 47.2 47.2 (Total PO) / PPE 1.3 1.3 1.6 1.6 (Total PO) / (PPE + FR) 0.9 0.9 1.0 1.0 PO (%) 27.6 27.6 38.4 38.4 PO / (PPE + FR) 0.5 0.5 0.8 0.8 Material property MFR, 250 占 폚, 10 kg (g / 10 min) 8.0 7.7 22.2 22.3 Flexural modulus (MPa) 501 388 182 126 Modulus of elasticity (MPa) 159.8 146.6 98.4 80.4 Shore A hardness 93.2 92.9 95 94 Tensile Stress (MPa) 13.9 13.6 12.6 10.9 Tensile elongation (%) 38.2 49.6 98 128 FOT UL94V, 3.2mm (sec) - - - 40.3 FOT UL94V, 6.4mm (sec) 172.6 37.4 100.2 10.6 / V1 Wire property VW-1, 2C / FOT (sec) F F F F VW-1, 1C / FOT (sec) F 13.3 F F Tensile Stress (MPa) 19.7 17.8 20.4 17.6 Tensile elongation (%) 117 130 170 187 Heat deformation, 121 ℃, 250g, 1h 9 12 7 10

Examples 10 to 25 and Comparative Examples 12 to 29

These samples illustrate that improved properties were obtained by substituting poly (arylene ether) -polysiloxane block copolymer reaction products for poly (arylene ether) in a composition using triaryl phosphate as a flame retardant.

The compositions were prepared and tested as described above. Composition and properties are summarized in Table 8.

Comparing the comparative example containing the poly (arylene ether) homopolymer and the corresponding embodiment of the present invention containing the poly (arylene ether) -polysiloxane block copolymer in terms of material properties, Lt; RTI ID = 0.0 &gt; flame retardancy. &Lt; / RTI &gt; Specifically, with respect to the flame stopping time in the UL94 vertical type combustion test determined at a sample thickness of 6.4 mm, Comparative Example 15 showed an average value of 25.2 seconds (UL94 V-1 rating) V0 grade); Comparative Example 16 showed an average value (UL94 V0 rating) of 6.3 seconds in Example 15 compared to an average value of 315.9 seconds (UL94 failure); Comparative Example 19 showed an average value (UL94 V0 rating) of 7.8 seconds in Example 16 compared to an average value of 289.0 seconds (UL94 failure); Comparative Example 21 showed an average value (UL94 V-1 rating) of 20.7 seconds in Example 17 compared to an average value of 277.8 seconds (UL94 failure); Comparative Example 22 exhibited an average value (UL94 V-1 rating) of 28.5 seconds in Example 18 compared to an average value of 268.5 seconds (UL94 failure); Comparative Example 23 exhibited an average value (UL94 V-1 rating) of 19.0 seconds in Example 19 compared to an average value of 174.0 seconds (UL94 failed); Comparative Example 24 showed an average value of 51.6 seconds in Example 20 as compared to an average value of 300.4 seconds (UL94 failed); Comparative Example 25 exhibited an average value (UL94 V-1 rating) of 23.5 seconds in Example 21 compared to an average value of 461.4 seconds (UL94 failure); Comparative Example 26 exhibited an average value (UL94 V0 rating) of 5.8 seconds in Example 22 compared to an average value of 201 seconds (UL94 failure); Comparative Example 27 exhibited an average value (UL94 V-1 rating) of 11.5 seconds in Example 23 compared to an average value of 288.9 seconds (UL94 failure); Comparative Example 28 showed an average value (UL94 V-1 rating) of 26.4 seconds in Example 24 compared to an average value of 133.6 seconds (UL94 failure); Comparative Example 29 showed an average value of 48.7 seconds (UL94 failure) in Example 25, while the average value of 240.9 seconds (UL94 failure) was shown.

By comparison of the comparative example containing the poly (arylene ether) homopolymer and the corresponding embodiment of the present invention containing the poly (arylene ether) -polysiloxane block copolymer, wire properties values were 13 No improvement was observed in 3 of the sample pairs, but exhibits improved VW-1 flammability. Specifically, with respect to the VW-1, 1C flame downtime, Comparative Example 12 failed the test while Example 10 showed an average combustion dwell time of 15.0 seconds; Comparative Example 13 showed an average value of 16.0 seconds, whereas Example 11 showed an average value of 8.3 seconds; Comparative Example 15 exhibited an average value of 15 seconds, and Example 14 showed an average value of 6 seconds and passed 2C VW-1 as compared to that of 2C VW-1, which means more robust FR performance in different wire configurations ; Comparative Example 16 failed the test while Example 15 showed a mean value of 9 seconds and passed the VW-1 / 2C; Comparative Example 19 failed the test while Example 16 showed an average value of 9 seconds and failed the test (note: the average flame stop time value can be calculated in some but not all failed samples); Comparative Example 21 failed the test while Example 17 showed an average value of 8.3 seconds and passed the VW-1 / 2C; Comparative Example 22 failed the test while Example 18 showed an average value of 6 seconds and passed the VW-1 / 2C; Comparative Example 23 failed the test while Example 19 showed an average value of 8 seconds and the test failed; Comparative Example 24 failed the test while Example 20 showed an average value of 10 seconds and the test failed; Comparative Example 25 failed the test while Example 21 showed an average value of 17 seconds and passed the VW-1 / 2C; Comparative Example 26 failed the test while Example 22 showed an average value of 5.3 seconds and passed the VW-1 / 2C.

Examples 26 to 30 and Comparative Examples 30 to 34

These samples have improved properties by substituting the poly (arylene ether) -polysiloxane block copolymer reaction product for the poly (arylene ether) in a composition using a flame retardant containing magnesium hydroxide optionally in combination with zinc borate .

The compositions were prepared and tested as described above. Composition and properties are summarized in Table 9.

Comparing the comparative example containing the poly (arylene ether) homopolymer and the corresponding embodiment of the present invention containing the poly (arylene ether) -polysiloxane block copolymer in terms of material properties, Lt; RTI ID = 0.0 &gt; tensile elongation &lt; / RTI &gt; and flame retardancy. Specifically, regarding the tensile elongation, Comparative Example 30 showed a value of 59%, while Example 26 showed a value of 67%; Comparative Example 31 showed a value of 98%, whereas Example 27 showed a value of 104%; Comparative Example 32 showed a value of 81%, whereas Example 28 showed a value of 110%; Comparative Example 33 showed a value of 84%, while Example 29 showed a value of 108%; Comparative Example 34 showed a value of 94%, whereas Example 30 showed a value of 109%. Regarding the flame dwell time for the UL94 vertical burn test at sample thickness 6.4 mm, Comparative Example 30 showed a mean value of 12.9 seconds for Example 26 compared to an average value of 38.7 seconds; Comparative Example 31 showed an average value of 10.4 seconds in Example 27 compared to an average value of 171.1 seconds; Comparative Example 32 showed an average value of 8.9 seconds in Example 28 compared to an average value of 144.1 seconds; Comparative Example 33 showed an average value of 8.4 seconds in Example 29 compared to an average value of 90.6 seconds; Comparative Example 34 shows an average value of 201.2 seconds, whereas the average value of 65.7 seconds in Example 30 was shown. The advantages of the embodiment of the present invention on UL 94 flame retardancy were not observed in the VW-1 test, and all the samples (embodiments of the invention and comparative examples) failed the VW-1 test.

This specification uses examples to disclose the invention, including the best mode, and to enable any person skilled in the art to make and use the invention. The patentability of the present invention is defined by the claims, and may include other embodiments that may be devised by those skilled in the art. Such alternative embodiments are intended to be included within the scope of the appended claims when they have structural elements that do not differ from the literal language of the claims.

All patents, patent applications and other references cited are hereby incorporated by reference in their entirety. However, where the terminology of the present specification is inconsistent with or conflicts with the terminology recited in the cited references, the terminology of this specification overrides the terminology that conflicts with the cited references.

All ranges disclosed herein include endpoints, and the endpoints can be merged independently of one another.

The use of the indefinite articles "a" and " an "and the like, and the like, and similar indications in connection with the description of the present invention (particularly in conjunction with the appended claims) Unless the context clearly dictates otherwise. Also, terms such as " first ", "second ", etc. used herein do not denote order, quantity, or importance, and are used to distinguish one element from another. The term "about" used in connection with any one quantity includes the stated value and means indicated by the context (including, for example, the degree of error associated with the measurement of a particular quantity).

Claims (27)

(Arylene ether) -polysiloxane block copolymer comprising a poly (arylene ether) homopolymer and a polysiloxane block comprising a poly (arylene ether) block and an average of 35 to 80 siloxane repeat units, (Arylene ether) -polysiloxane block copolymer reaction product 5 to 55 wt%;
10 to 55% by weight hydrogenated block copolymer of a conjugated diene with an alkenyl aromatic compound; And
2 to 25 wt%
&Lt; / RTI &gt;
Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product comprises 1-8 wt% siloxane repeat units and 92-99 wt% arylene ether repeat units;
Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product is a product of a process comprising oxidizing a monomer mixture comprising a monovalent phenol and a hydroxyaryl-terminated polysiloxane in an oxidative manner;
The poly (arylene ether) -polysiloxane block copolymer reaction product has a weight average molecular weight of 30,000 atomic mass units or more;
Here, except for the content unit of the siloxane repeating unit and the arylene ether repeating unit Wherein all of the weight percentages are based on the total weight of the composition. The method according to claim 1,
Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product has a weight average molecular weight of from 30,000 to 150,000 atomic mass units. 3. The method according to claim 1 or 2,
Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product comprises less than 25% by weight of molecules having a molecular weight of less than 10,000 atomic mass units. The method of claim 3,
Wherein said molecule having a molecular weight less than 10,000 atomic mass units comprises an average of 5 to 10 weight percent siloxane repeat units. The method according to claim 1,
Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product comprises less than 25% by weight of molecules having a molecular weight greater than 100,000 atomic mass units. 6. The method of claim 5,
Wherein said molecule having a molecular weight greater than 100,000 atomic mass units comprises an average of 3-6% siloxane repeat units. The method according to claim 1,
Wherein the monohydric phenol is composed of 2,6-dimethylphenol,
Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product comprises up to 0.4% by weight of a 2,6-dimethylphenoxy group. The method according to claim 1,
Wherein the poly (arylene ether) block comprises an arylene ether repeat unit having the structure:

Wherein in each repeating unit, each Z ¹ is independently halogen, Beach cyclic or substitutional C ₁ -C ₁₂ hydrocarbyl, with the proviso that the hydrocarbyl group is not a tertiary hydrocarbyl, C ₁ - C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbyloxy, or C ₂ -C ₁₂ halo hydrocarbyloxy, wherein two or more carbon atoms separate hydrogen and oxygen atoms; Each Z ² is independently hydrogen, halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl, provided that the hydrocarbyl group is not a tertiary hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbyloxy, or C ₂ -C ₁₂ halo hydrocarbyloxy, wherein two or more carbon atoms separate hydrogen and oxygen atoms,
Wherein the polysiloxane block comprises a repeating unit having the structure:

In the formula, each R ¹ and R ² is, independently, hydrogen, C ₁ -C ₁₂ hydrocarbyl or C ₁ -C ₁₂ halohydrocarbyl,
Wherein the polysiloxane block further comprises a termination unit having the structure:

Formula, Y is hydrogen, C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbyl-oxy, or halogen, each of R ³ and R ⁴ are independently hydrogen, C ₁ -C ₁₂ hydrocarbyl Or C ₁ -C ₁₂ halohydrocarbyl. The method according to claim 1,
Wherein the poly (arylene ether) block comprises an arylene ether repeat unit having the structure:

Wherein said polysiloxane block has the structure:

In the formula, n is an integer of 35 to 60,
Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product has a number average molecular weight of from 10,000 to 30,000 atomic mass units. The method according to claim 1,
Wherein the composition comprises 25-42 wt% of the poly (arylene ether) -polysiloxane block copolymer reaction product; Wherein the poly (arylene ether) block comprises an arylene ether repeat unit having the structure:

Wherein said polysiloxane block has the structure:

In the formula, n is an integer from 35 to 60;
Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product has a number average molecular weight of from 10,000 to 30,000 atomic mass units;
Said composition comprising from 20 to 41% by weight of said hydrogenated block copolymer; Wherein the hydrogenated block copolymer comprises a polystyrene-poly (ethylene-butylene-styrene) -polystyrene triblock copolymer and a polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer;
Said composition comprising 6 to 16% by weight of said flame retardant; Wherein the flame retardant comprises triaryl phosphate;
Said composition comprising from 25 to 45% by weight of total polyolefin; Wherein the total polyolefin consists of a polyolefin, a polyolefin block in the block copolymer, and a polyolefin skeleton and graft in the graft copolymer;
Wherein the total ratio of said total polyolefin to said flame retardant and said poly (arylene ether) -polysiloxane block copolymer reaction product is from 0.6: 1 to 0.9: 1. 11. The method of claim 10,
3 to 15% by weight polybutene. 11. The method of claim 10,
3 to 15% by weight polypropylene. An extruded or injection molded article comprising a product obtained by extrusion or injection molding the composition,
Wherein the composition comprises
Polysiloxane block copolymer comprising a poly (arylene ether) homopolymer and a polysiloxane block comprising a poly (arylene ether) block and an average of 35 to 80 siloxane repeat units, 5 to 55% by weight poly (arylene ether) -polysiloxane block copolymer reaction product;
From 10 to 50% by weight of a hydrogenated block copolymer of a conjugated diene with an alkenyl aromatic compound; And
2 to 20% by weight of a flame retardant,
Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product comprises 1-8 wt% siloxane repeat units and 92-99 wt% arylene ether repeat units;
Wherein the poly (arylene ether) -polysiloxane block copolymer reaction product is a product of a process comprising oxidizing a monomer mixture comprising a monovalent phenol and a hydroxyaryl-terminated polysiloxane in an oxidative manner;
The poly (arylene ether) -polysiloxane block copolymer reaction product has a weight average molecular weight of 30,000 atomic mass units or more;
Wherein all said weight percentages, excluding the content units with respect to the siloxane repeat units and the arylene ether repeat units, are based on the total weight of said composition. 14. The method of claim 13,
Wherein the extruded or injection molded article comprises a coated wire comprising a conductor and a covering disposed on the conductor; Wherein the covering comprises the composition. delete delete delete delete delete delete delete delete delete delete delete delete delete